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Jozef H. Meessen, DSM Stamicarbon, Geleen, The Netherlands (Chaps. 1 – 7) Harro Petersen, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany (Chap. 8) 1. 2. 3. 3.1. 3.1.1. 3.1.2. 3.2. 3.2.1. 3.2.2. 3.2.3. 3.3. 3.3.1. 3.3.2. 126.96.36.199. 188.8.131.52. 184.108.40.206. 220.127.116.11. 3.3.3. 3.4. 3.5. 4. 5. Physical Properties . . . . . . . . . . Chemical Properties . . . . . . . . . Production . . . . . . . . . . . . . . . Principles . . . . . . . . . . . . . . . . Chemical Equilibrium . . . . . . . . Physical Phase Equilibria . . . . . . Challenges in Urea Production Process Design . . . . . . . . . . . . Recycle of Nonconverted Ammonia and Carbon Dioxide . . . . . . . . . . Corrosion . . . . . . . . . . . . . . . . Side Reactions . . . . . . . . . . . . . Description of Processes . . . . . . Conventional Processes . . . . . . . . Stripping Processes . . . . . . . . . . Stamicarbon CO2 -Stripping Process Snamprogetti Ammonia- and Self-Stripping Processes . . . . . . . ACES Process . . . . . . . . . . . . . Isobaric Double-Recycle Process . Other Processes . . . . . . . . . . . . Efﬂuents and Efﬂuent Reduction Product-Shaping Technology . . . Forms Supplied, Storage, and Transportation . . . . . . . . . . . . Quality Speciﬁcations and Analysis . . . . . . . . . . . . . . . . . 2 3 4 4 4 7 8 9 11 12 13 13 13 13 16 18 19 19 20 21 22 23 6. 7. 8. 8.1. 8.2. 8.2.1. 8.2.2. 8.2.3. 8.2.4. 8.2.5. 8.2.6. 8.2.7. 8.3. 8.3.1. 8.3.2. 8.3.3. 8.3.4. 9. Uses . . . . . . . . . . . . . . . . . . . Economic Aspects . . . . . . . . . . Urea Derivatives . . . . . . . . . . . Thermal Condensation Products of Urea . . . . . . . . . . . . . . . . . . Alkyl- and Arylureas . . . . . . . . Transamidation of Urea with Amines . . . . . . . . . . . . . . . . . . Alkylation of Urea with Tertiary Alcohols . . . . . . . . . . . . . . . . . Phosgenation of Amines . . . . . . . Reaction of Amines with Cyanates (Salts) . . . . . . . . . . . . . . . . . . Reaction with Isocyanates . . . . . . Acylation of Ammonia or Amines with Carbamoyl Chlorides . . . . . . Aminolysis of Esters of Carbonic and Carbamic Acids . . . . . . . . . . Reaction of Urea and Its Derivatives with Aldehydes . . . . α-Hydroxyalkylureas . . . . . . . . . α-Alkoxyalkylureas . . . . . . . . . . α,α -Alkyleneureas . . . . . . . . . . Cyclic Urea – Aldehyde Condensation Products . . . . . . . . References . . . . . . . . . . . . . . . 24 24 25 25 25 25 26 26 27 27 27 27 28 28 29 30 31 33
Abbreviations: CRH, % critical relative humidity ∆H S , kJ/mol integral heat of solution m, mol/kg urea molality, moles of urea per kilogram of water PO 2 , Pa water vapor pressure of a satu(s)H rated urea solution Pv , Pa vapor pressure Urea [57-13-6], CO(NH2 )2 , M r 60.056, plays an important role in many biological processes, among others in decomposition of proteins. The human body produces 20 – 30 g of urea per day. ¨ In 1828, Wohler discovered  that urea can be produced from ammonia and cyanic acid in aqueous solution. Since then, research on the
c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a27 333
preparation of urea has continuously progressed. The starting point for the present industrial production of urea is the synthesis of Basaroff , in which urea is obtained by dehydration of ammonium carbamate at increased temperature and pressure:
NH2 COONH4 CO(NH2 )2 + H2 O
In the beginning of this century, urea was produced on an industrial scale by hydration of cyanamide, which was obtained from calcium cyanamide:
CaCN2 + H2 O + CO2 → CaCO3 + CNNH2 CNNH2 + H2 O → CO(NH2 )2
Urea The vapor pressure of the solid phase between 56 and 130 ◦ C  can be calculated from
lnPv = 32.472 − 11 755/T
After development of the NH3 process (Haber and Bosch, 1913, →Ammonia, Chap. 2. →Ammonia, Chap. 3. →Ammonia, Chap. 4.), the production of urea from NH3 and CO2 , which are both formed in the NH3 synthesis, developed rapidly:
2 NH3 + CO2 NH2 COONH4 NH2 COONH4 CO(NH2 )2 + H2 O
Hygroscopicity. The water vapor pressure of a saturated solution of urea in water PO 2 in (s)H the temperature range 10 – 80 ◦ C is given by the relation 
lnP(s)H2 O = 175.766 − 11 552/T − 22.679 lnT
At present, urea is prepared on an industrial scale exclusively by reactions based on this reaction mechanism.
By starting from the vapor pressure of pure water PO2 , the critical relative humidity (CRH) then H can be calculated as
CRH = P(s)H2 O /PH2 O 100
1. Physical Properties , 
Pure urea forms white, odorless, long, thin needles, but it can also appear in the form of rhomboid prisms. The crystal lattice is tetragonal – scalenohedral; the axis ratio a : c=1 : 0.833. The urea crystal is anisotropic (noncubic) and thus shows birefringence. At 20 ◦ C the refractive indices are 1.484 and 1.602. Urea has an mp of 132.6 ◦ C; its heat of fusion is 13.61 kJ/mol. Physical properties of the melt at 135 ◦ C follow:
Molecular volume η Kinematic viscosity Molar heat capacity, Cp Speciﬁc heat capacity, cp Surface tension 1247 kg/m3 48.16 m3 /kmol 3.018 mPa · s 2.42×10−6 m2 /s 135.2 J mol−1 K−1 2.25 kJ kg−1 K−1 66.3×10−3 N/m
The CRH is a threshold value, above which urea starts absorbing moisture from ambient air. It shows the following dependence on temperature:
25 ◦ C 30 ◦ C 40 ◦ C 76.5 % 74.3 % 69.2 %
At 25 ◦ C, in the range of 0 – 20 mol of urea per kilogram of water, the integral heat of solution of urea crystals in water ∆H s as a function of molality m is given by :
∆Hs = 15.351 − 0.3523m + 2.327 · 10−2 m2 −1.0106 · 10−3 m3 + 1.8853 · 10−5 m4
In the temperature range 133 – 150 ◦ C, density and dynamic viscosity of a urea melt can be calculated as follows:
r = 1638.5 − 0.96 T lnη = 6700/T − 15.311
Urea forms a eutectic mixture with 67.5 wt % of water with a eutectic point at −11.5 ◦ C. The solubility of urea in a number of solvents, as a function of temperature is summarized in Table 1 , .
The density of the solid phase at 20 ◦ C is 1335 kg/m3 ; the temperature dependence of the density is given by 0.208 kg m−3 K−1 . At 240 – 400 K, the molar heat capacity of the solid phase is 
Cp = 38.43 + 4.98 × 10−2 T + 7.05 × 10−4 T 2 − 8.61 × 10−7 T 3
2. Chemical Properties
Upon heating, urea decomposes primarily to ammonia and isocyanic acid. As a result, the gas phase above a urea solution contains a considerable amount of HNCO, if the isomerization reaction in the liquid phase
CO(NH2 )2 NH4 NCO NH3 + HNCO
Table 1. Solubility of urea in various solvents (solubility in wt % of urea) Temperature, ◦ C Solvent Water Ammonia Methanol Ethanol 0 39.5 34.9 13.0 2.5 20 51.8 48.6 18.0 5.1 40 62.3 67.2 26.1 8.5 60 71.7 78.7 38.6 13.1 80 80.2 84.5 100 88.1 90.4
has come to equilibrium . In dilute aqueous solution, the HNCO formed hydrolyzes mainly to NH3 and CO2 . In a more concentrated solution or in a urea melt, the isocyanic acid reacts further with urea, at relatively low temperature, to form biuret (NH2 – CO – NH – CO – NH2 ), triuret (NH2 – CO – NH – CO – NH – CO – NH2 ), and cyanuric acid (HNCO)3 . At higher temperature, guanidine [CNH(NH2 )2 ], ammelide [C3 N3 (OH)2 NH2 ], ammeline [C3 N3 OH(NH2 )2 ], and melamine [C3 N3 (NH2 )3 ] are also formed , . Melamine can also be produced from urea by a catalytic reaction in the gas phase. To this end, urea is decomposed into NH3 and HNCO at low pressure, and subsequently transformed catalytically to melamine (→Melamine and Guanamines, Chap. 4.). Urea reacts with NOx , both in the gas phase at 800 – 1150 ◦ C and in the liquid phase at lower temperature, to form N2 , CO2 , and H2 O. This reaction is used industrially for the removal of NOx from combustion gases , . Reactions with Formaldehyde. Under acid conditions, urea reacts with formaldehyde to form among others, methyleneurea, as well as dimethylene-, trimethylene-, tetramethylene-, and polymethyleneureas. These products are used as slow-release fertilizer under the generic name ureaform  (→Fertilizers, Chap. 18.104.22.168.). The reaction scheme for the formation of methyleneurea is given below:
The reactions of urea with formaldehyde under basic conditions are used widely for the production of synthetic resins (→Amino Resins, Chap. 7.1.). As a ﬁrst step, methylolurea instead of methyleneurea is formed:
This product subsequently reacts with formaldehyde to dimethylol urea, CO(NHCH2 OH)2 , and further polymerization products. Since urea is also the raw material for the production of melamine, from which melamine – formaldehyde resins are produced, it is the most important building block in the production of amino resins. When urea is applied as fertilizer to soil, it hydrolyzes in the presence of the enzyme urease to NH3 and CO2 , after which NH3 is bacteriologically converted into nitrate and, as such, absorbed by crops .
3.1.1. Chemical Equilibrium
Methyleneurea reacts with additional molecules of formaldehyde to yield dimethyleneurea and other homologous products.
In all commercial processes, urea is produced by reacting ammonia and carbon dioxide at elevated temperature and pressure according to the Basaroff reactions:
goes Figure 3. H2 O: CO2 ratio = 0. Ammonia conversion at chemical equilibrium as a function of temperature NH3 : CO2 ratio = 3.4 Urea 2 NH3 (l) + CO2 (l) ∆H =− 117 kJ/mol NH2 COONH4 NH2 CONH2 + H2 O (2) NH2 COONH4 (1) ∆H =+ 15. In the ﬁrst reaction. Since more heat is produced in the ﬁrst reaction than consumed in the second. Physical and chemical equilibria in urea production Figure 2.. temperature. the overall reaction is exothermic. ammonium carbamate dehydrates to produce urea and water. Carbon dioxide conversion at chemical equilibrium as a function of temperature NH3 : CO2 ratio = 3. the reaction is fast and exothermic. H2 O: CO2 ratio = 0. and pressure) at which these reactions are carried out. This effect is usually attributed to the fact that the ammonium carbamate concentration as a function of temperature goes through a maximum. CO2 . the methods correspond closely to each other: The achievable conversion per pass. This maximum in the ammonium carbamate concentration can be explained. Traditionally.5 mol/mol (initial mixture). First attempts to describe the chemical equilibrium of Reactions (1) and (2) were made by Frejacques . However. by the respective heat effects of Reactions (1) and (2). this mechanism cannot explain the observed conversion maximum fully and quantitatively. . which is slow and endothermic. the hypothetical mixture consisting only of NH3 . at least qualitatively.  and thermodynamically consistent analyses of the equilibria . through a maximum (Figs. 2 and 3).25 mol/mol (initial mixture) The inﬂuence of the composition of the initial mixture on the chemical equilibrium can be explained qualitatively by Reactions (1) and (2) and the law of mass action: . As far as the most important consequences of these equilibria on urea process design are concerned. dictated by the chemical equilibrium as a function of temperature. the composition of the liquid phase in the reaction zone is expressed by two molar ratios: usually. Later descriptions of the chemical equilibria can be divided into regression analyses of measurements .25 mol/mol (initial mixture) Processes differ mainly in the conditions (composition. Both reﬂect the composition of the so-called initial mixture [i. and H2 O if both Reactions (1) and (2) are shifted completely to the left]. other contributing mechanisms have been suggested . Figure 1. the molar NH3 : CO2 and the molar H2 O : CO2 ratios. carbon dioxide and ammonia are converted to ammonium carbamate.e.5 kJ/mol A schematic of the overall process and the physical and chemical equilibria involved is shown in Figure 1.5 mol/mol (initial mixture). In the second rection.
In these cases. Historically. e. this may be justiﬁed by the fact that in early urea processes. it is based on the arbitrary choice of CO2 as the key component. not yet fully understood reaction mechanisms probably contribute to the chemical equilibria to a minor extent. NH3 : CO2 ratio = 3. Figs. Ammonia conversion at chemical equilibrium as a function of H2 O : CO2 ratio T = 190 ◦ C. but reduces NH3 conversion (Figs.g. and 6. however. For the present generation of stripping processes. that is. a full quantitative description cannot be derived simply from the law of mass action and Reactions (1) and (2). H2 O : CO2 ratio = 0. the amount of CO2 in the initial mixture converted into urea (plus biuret). This way of representing the chemical equilibrium is consistent with the presentation usually found in the traditional urea literature. the conversion at chemical equilibrium is expressed as CO2 conversion.25 mol/mol (initial mixture) In Figures 2. H2 O : CO2 ratio = 0. if no changes occur in overall NH3 .5 mol/mol (initial mixture) Figure 4. NH3 : CO2 ratio = 3. CO2 .5 mol/mol (initial mixture) Figure 5. Carbon dioxide conversion at chemical equilibrium as a function of H2 O : CO2 ratio T = 190 ◦ C.Urea 1) Increasing the NH3 : CO2 ratio (increasing the NH3 concentration) increases CO2 conversion. Comparing. CO2 conversion was more important than NH3 conversion. 5 Figure 6. 2) Increasing the amount of water in the initial mixture (increasing the H2 O : CO2 ratio) results in a decrease in both CO2 and NH3 conversion (Figs. Ammonia conversion at chemical equilibrium as a function of NH3 : CO2 ratio T = 190 ◦ C. Other. . However. 4.25 mol/mol (initial mixture) Figure 7. too. Carbon dioxide conversion at chemical equilibrium as a function of NH3 : CO2 ratio T = 190 ◦ C. and H2 O concentrations in the liquid phase. giving a higher weight to CO2 conversion is not justiﬁed. 4 and 5).. 6 and 7). 4 and 5.
. Figure 8. the concentration of urea in the liquid phase) is a better tool for judging optimum process parameters than CO2 or NH3 conversion. Physical Phase Equilibria In urea production. shows that an arbitrary choice of one of the two feedstock components as yardstick to evaluate optimum reaction conversion can easily lead to faulty conclusions. Figure 8 illustrates that urea yield as . Figure 10 shows that the urea yield as a function of NH3 : CO2 ratio reaches a maximum somewhat above the stoichiometric ratio (2 : 1). The chemical interaction between NH3 and CO2 (mainly the formation of ammonium carbamate) results in a strongly azeotropic behavior of the “binary” system NH3 – CO2 . thus.6 Urea a function of temperature also goes through a maximum.5 mol/mol (initial mixture) Ultimately.e. An approach to the description of the phase equilibria if urea and water are added to the NH3 – CO2 system was given by Kaasenbrood and Chermin . i. one can argue that the urea yield (i. the phase behavior of the components under synthesis conditions is important.5 mol/mol (initial mixture). one of the targets in designing a recycle system must be to minimize water recycle. Urea yield in the liquid phase at chemical equilibrium as a function of H2 O : CO2 ratio T = 190 ◦ C. Urea yield in the liquid phase at chemical equilibrium as a function of NH3 : CO2 ratio T = 190 ◦ C. Without going into such time. H2 O : CO2 ratio = 0. Another important reason for this can be found from the physical phase equilibria in the NH3 – CO2 – H2 O – urea system. both components are in the supercritical state.and place-dependent economic considerations. In all commercial processes.1. conditions are such that pressure and temperature are well above the critical conditions of the feedstocks ammonia and carbon dioxide.25 mol/mol (initial mixture) Figure 10.e. NH3 : CO2 ratio = 3. If Figure 9.25 mol/mol (initial mixture) 3.. This is one of the reasons that all commercial processes operate at NH3 : CO2 ratios above the stoichiometric ratio. H2 O: CO2 ratio = 0. Urea yield in the liquid phase at chemical equilibrium as a function of temperature NH3 : CO2 ratio = 3.2. project economics (investment and consumptions) will dictate the choice of process parameters in the reaction section. Figure 9 again shows the detrimental effect of excess water on urea yield. the location of this maximum is of course composition dependent.
Most important items are product quality. The points on this line do not have the same A : B ratio as the maximum for the binary azeotrope. then the T – X liquid and gas planes for the ternary system thus formed assume a special shape owing to the peculiar path described by the boiling points of the changing solutions (Fig. In some processes. 3. The pressure is such that both A and B are supercritical. partly conﬂicting. the equilibria in the NH3 – CO2 – H2 O – urea system under urea synthesis conditions show a maximum in temperature at a given pressure as a function of NH3 : CO2 ratio. Liquid – gas equilibrium in a ternary system with binary azeotrope at constant pressure The system A – B forms a binary azeotrope. Challenges in Urea Production Process Design Like any process design. the NH3 : CO2 ratio in all commercial processes is chosen well above the stoichiometric ratio (2 : 1). this difference in solubility also causes the pressure minimum (or temperature maximum) to shift toward higher NH3 : CO2 ratios as the amount of solvent (water and urea) increases.Urea a less volatile solvent C (water) is added to an azeotropic system A – B (NH3 – CO2 ) at a pressure where both components A and B are supercritical. C is a solvent for both A and B. Carbon dioxide is less soluble than ammonia in water and urea melts. reliability of operation and a low initial investment. . Figure 11. Moreover. are of practical importance in the realization of commercial urea processes. A full description of the phase equilibria in this system is even more complex than the aforementioned hypothetical A – B – C system. Also resulting from the age of urea process design is the observation that a process can only be successful if acceptable and competing solutions to all of these criteria can be combined into one process design. it will be clear that compromises between the aforementioned. Apart from applying straightforward normal engineering approaches. If the peak points of this ridge are linked up. the top ridge line is obtained. environmental aspects. As a result. The A : B ratio changes and the boiling point increases as the percentage of C increases. because A and B are not soluble in solvent C to the same extent. a urea plant design has to fulﬁl a number of criteria. whereas the pressure is below the critical pressure of C. the pressure gradient at constant temperature is much steeper on the CO2 -rich side of the top ridge line. Since the urea process already has half a century of commercial scale history. this means that in order to achieve relatively low pressures at a given temperature. whereas in other processes an even greater excess of ammonia is used.. at a ratio of ca. this ratio is chosen on the pressure minimum (on the top ridge line. 7 Analogous to the description of Figure 11. Sections through the liquid plane for constant solvent content are analogous to the liquid line for the binary system. and the associated temperature maximum (or pressure minimum) in the ternary and quaternary systems with water and urea. i. 11). 3 : 1). The strongly azeotropic behavior of the NH3 – CO2 system. feedstocks and utilities consumptions. The liquid plane for the ternary systems appears as a ridge in the T – X space. Practically. since the solid – liquid (S – L) and solid – gas (S – G) equilibria interfere with the liquid – gas (L – G) equilibria.2.e. criteria are well established. safety.
a relatively simple urea process scheme was realized. 7. the heat supplied to the urea synthesis solution was used only once. focuses in urea plant design essentially on a few peculiarities: 1) The thermodynamic limit on the conversion per pass through the urea reactor.3. necessitates a cunning recycle system design. The energy balance of the conventional processes is shown in Figure 13. Stripping Processes.1 indicates that the conversion of the feedstocks NH3 and CO2 to urea is limited. at low pressure (2 – 5 bar). In this ﬁrst-generation urea process. nitric acid) to produce ammonium salts (such as ammonium nitrate) as coproducts of urea production. 3) The occurrence of two side reactions – hydrolysis of urea and biuret formation – must be considered. Figure 12 is a typical ﬂow sheet . nonconverted NH3 was neutralized with acids (e. Characteristic of these processes is that the major part of the recycle of both nonconverted NH3 and nonconverted CO2 occurs via the gas phase. Once-Through Processes. from which relatively pure NH3 (at the top) and a bottom product consisting of an aqueous ammonium carbamate solution were obtained. several licensors developed schemes in which the recirculation of nonconverted NH3 and CO2 was performed in two stages. 2) The intermediate product ammonium carbamate is extremely corrosive.1.3). the challenge of ﬁnding an optimum synergy between partly conﬂicting criteria.2. see Section 3. all nonconverted CO2 was recycled as an aqueous solution. In this way. the Stamicarbon CO2 -stripping process was developed. where essentially all of the nonconverted ammonia and carbon dioxide were recycled to the urea reactor. Such a process required about 1. The main disadvantages of the once-through processes are the large quantity of ammonium salt formed as coproduct and the limited amount of overall carbon dioxide conversion that can be achieved. and equipment design is therefore essential. Another characteristic difference between conventional and stripping processes in terms of the recycle scheme. 3. 6. have survived until now (see Section 3. Because of the detrimental effect of water on reaction conversion (see Figs. All conventional processes therefore typically operate at high NH3 : CO2 ratios (4 – 5 mol/mol) to maximize CO2 conversion per pass. while excess NH3 evaporates simultaneously. can be found in the way heat is supplied to the recirculation zones.1. such that none of these recycles is associated with a large water recycle to the synthesis zone. Recycle of Nonconverted Ammonia and Carbon Dioxide The description of the chemical equilibria in Section 3. achieving a minimum CO2 recycle (and thus maximum CO2 conversion per reaction pass) was much more important than achieving a low NH3 recycle..3. In the 1960s. whereas the main portion of nonconverted NH3 was recycled without an associated water recycle. Although some of these conventional processes.1). An important differentiator between processes is the way these nonconverted materials are handled. this type of process can be referred to as an N = 1 process. A proper combination of process conditions. construction materials. and 9). In the very ﬁrst processes. The off-gas from this ﬁrst decomposition step was subjected to rectiﬁcation (e).2). partly equipped with ingenious heat-exchanging networks. therefore. The ﬁrst recirculation stage was operated at medium pressure (18 – 25 bar). A peculiar aspect of this historic development is a partial “revival” of these combined urea – ammonium nitrate production facilities (UAN plants. now called conventional. the second. their importance decreased rapidly as the so-called stripping processes were developed.8 Urea of these. followed later by other processes (see Section 3.g. Oncethrough processes were soon replaced by totalrecycle processes. Conventional Recycle Processes. In the ﬁrst generation of total-recycle processes. combined with the azeotropic behavior of the NH3 – CO2 system. In these processes.3. Both products are reycled separately to the urea reactor (c). The ﬁrst recirculation stage comprises at least a decomposition heater (d). in which carbamate decomposes into gaseous NH3 and CO2 . processes.8 t of steam per tonne of urea.
including the energy supply to the carbon dioxide compressor drive. d) Medium-pressure decomposer. Typical ﬂow sheet of a conventional urea plant a) CO2 compressor.Urea 9 Figure 12. Figure 14. As can be seen from Figures 14 and 15. This heat is recovered in a highpressure carbamate condenser (unconverted ammonia and carbon dioxide are condensed to form ammonium carbamate) and reused in the lowpressure heaters. j) Vacuum condensation section Figure 13. the steam requirement for process heating is reduced in these types of processes. The heat supplied is effectively used twice. e) Ammonia – carbamate separation column. a distinct difference in the heat balance with respect to the conventional process is that only the heat in the ﬁrst heater (the high-pressure stripper) is imported. some processes were described that aim at a greater reduction of energy consumption by a further application of this multiple effect to N = 3 (Fig. Conceptual diagram of the heat balance of a conventional urea process Heat to each subsequent heater is supplied in the form of steam. the term N = 2 process is used. The energy balance of a stripping plant is shown in Figure 14. g) Evaporator. are taken into consideration . f) Low-pressure decomposer. b) High-pressure ammonia pump. As in conventional plants. if the full capabilities of a N = 2 type of process are exploited and if the total energy supply scheme. c) Urea reactor. whether the total energy consumption for the process is also reduced is doubtful. Conceptual diagram of the heat balance of a stripping plant Heat supplied to the ﬁrst heater (the stripper) is recovered in the ﬁrst condenser (high-pressure carbamate condenser) and subsequently used again in the low-pressure heaters (decomposers and water evaporators). i) Desorber (wastewater stripper). In the 1980s. However.0 t of steam per tonne of urea. thus. h) Prilling. it seems that the emphasis in urea technology now is shifting from low energy consumption toward other . heat must be supplied to the urea synthesis solution to decompose unconverted carbamate and to evaporate excess ammonia and water. 15) [25–29]. Moreover.8 – 1. the heat is effectively used twice (N = 2). the heat is used only once (N = 1). However. The average energy consumption of the stripping process is 0.
Stainless steel exposed to carbamatecontaining solutions involved in urea synthesis can be kept in a passivated (noncorroding) state by a given quantity of oxygen. equipment manufacture and inspection. Role of Oxygen Content. This accounts for the severe corrosion sometimes observed in cold spots inside gas lines. Awareness of the important factors in material selection. and simple process design . Not only condensing but also stagnant conditions are dangerous. An increase in temperature increases active corrosion.10 Urea layer. Although some alternatives have been mentioned . This is necessary because – notwithstanding the presence of oxygen in the gas phase – an oxygen-deﬁcient corrosive condensate is initially formed on condensation. Role of Temperature and Other Process Parameters in Corrosion. Stainless steel in a corrosive medium owes its corrosion resistance to the presence of a protective oxide layer on the metal.) 0. Corrosion  Urea synthesis solutions are very corrosive. The higher-alloyed austenitic stain- factors. When condensation constitutes an essential process step – for example. especially where narrow crevices are present. above a critical temperature it causes spontaneous activation of passive steel. Further heat integration of a stripping plant in conceptual form Heat supplied to the ﬁrst heater (the stripper) is effectively used three times (N = 3). but more important. Since the liquid phase in urea synthesis behaves as an electrolyte. Hence. technological design and proper operations of the plant.2. introduction of oxygen and maintenance of a sufﬁciently high oxygen content in the various process streams are prerequisites to preventing corrosion of the equipment. In this condensate the oxygen is absorbed only slowly. Passive corrosion rates of austenitic urea-grade stainless steels are generally between <0. This follows from the observation that carbamate-containing product streams are corrosive whereas pure urea solutions are not. while appropriate liquid – gas distribution devices ensure that no dry spots exist on condensing surfaces. activation and. corrosion starts after some time – its onset depending on process conditions and the quality of the passive layer.10 mm/a. The trouble can be remedied by adequate isolation and tracing of the lines. . As long as this layer is intact. Temperature is the most important technological factor in the behavior of the steels employed in urea synthesis. The corrosiveness of the synthesis solution has forced urea manufacturers to set very strict demands on the quality and composition of construction materials. If the oxygen content drops below this limit. Figure 15.2. the metal corrodes at a very low rate.01 and (max. These measures can involve ensuring that an oxygenrich liquid phase is introduced into the condenser. Upon removal of the oxide layer. From the point of view of corrosion prevention. 3. into which hardly any oxygen can penetrate and oxygen depletion may occur. together with periodic inspections and nondestructive testing are the key factors for safe operation for many years. corrosion set in unless the medium contains sufﬁcient oxygen or oxidation agent to build a new . Active corrosion rates can reach values of 50 mm/a. the condensation of NH3 – CO2 – H2 O gas mixtures to carbamate solutions deserves great attention. such as more durable construction materials. consequently. the use of oxygen to inﬂuence the redox potential has become common practice in urea manufacture ever since it was initially suggested . ammonium carbamate is considered the aggressive component. Generally. the corrosion it causes is of an electrochemical nature. more modern process control systems. . in high-pressure and low-pressure carbamate condensers – special technological measures must be taken.
In the Snamprogetti stripping processes. Like all Cr-containing stainless steels. weldability.. but still fully austenitic stainless steel (25 Cr 22 Ni 2 Mo) was chosen as construction material for the stripper tubes. 3. duplex alloys (ferritic – austenitic) are used as construction material for the stripper tubes. these results depend on the speciﬁc temperature and oxygen content during the experiments. In downstream sections of the plant. workability. in all downstream sections of the plant the NH3 and CO2 concentrations in urea-containing solutions are such that Reaction (3) is shifted to the right. as well as economic considerations such as price. Other factors such as mechanical properties.2. In stripping processes. and weldability. Experiments have showed that under practical conditions this inﬂuence is not measurable because the steel retains passivity. NH3 is removed from the urea solutions. At low and high ratios.3. The extent to which biuret is formed is determined by reaction kinetics. The extent to which the reaction occurs is determined by temperature (high temperatures favor hydrolysis) and reaction kinetics. Side Reactions  Three side reactions are of special importance in the design of urea production processes: Hydrolysis of urea CO(NH2 )2 + H2 O → NH2 COONH4 → 2 NH3 + CO2 (3) Biuret formation from urea: 2 CO(NH2 )2 → NH2 CONHCONH2 + NH3 (4) Formation of isocyanic acid from urea: CO(NH2 )2 → NH4 NCO → NH3 + HNCO (5) All three side reactions have in common the decomposition of urea. and delivery time. the extent to which they occur must be minimized. therefore. Reaction (5) shows that formation of isocyanic acid from urea is also favored by low NH3 concentrations. a higher-alloyed. The biuret reaction (4) also approaches equilibrium in the urea reactor . to purify this gas or the CO2 thoroughly. the practical measures to minimize biuret formation are the same as described above for the hydrolysis reaction. even when activated electrochemically. the process conditions in the high-pressure stripper are most severe with respect to corrosion. such that only a small amount of biuret is formed in the reactor. 22 wt % nickel. reparability. this means that retention times of urea-containing solutions at high temperatures must be minimized. Whereas this reaction approaches equilibrium in the reactor. in practice. availability. and the cheaper price of stainless steel-type materials. titanium usually is chosen for this critical application. This reaction is especially . also deserve attention. The higher-alloyed steel type 25 Cr 22 Ni 2 Mo showed stable passivity.Urea less steels (e. . Stainless steels that have found wide use are the austenitic grades AISI 316 L and 317 L. thus. thereby creating a driving force for biuret formation. In the ACES process. Hence it is imperative in plants using the 316 L and 317 L grades in combination with CO2 derived from sulfur-containing gas. The hydrolysis reaction (3) is nothing but the reverse of urea formation. Material Selection. In the Stamicarbon CO2 -stripping process. the NH3 : CO2 ratio in synthesis solutions is also claimed to have an inﬂuence on the corrosion rate of steels under urea synthesis conditions.g. irrespective of the NH3 : CO2 ratio. Corrosion resistance is not the only factor determining the choice of construction materials. Of course. This choice ensures better corrosion resistance than 316 L or 317 L types of material but still maintains the advantages of workability. The high NH3 concentration in the reactor shifts Reaction (4) to the left. 316 L stainless steel could not be activated. containing 25 wt % chromium. and 2 wt % molybdenum) appear to be much less sensitive to this critical temperature than 316 L types of steel. Only with electrochemical activation could 316 L types of steel be activated at intermediate NH3 : CO2 ratios. AISI 316 L and 317 L are not resistant to the action of sulﬁdes. . although mechanically bonded bimetallic 25 Cr 22 Ni 2Mo – zirconium tubes have also 11 been suggested to improve corrosion resistance . Sometimes. Spontaneous activation did not occur.
To realize maximum urea yield per pass through the reactor at the stipulated optimum pressure of 140 bar. Together with the relatively high temperatures in the evaporators.3. The greater part of the unconverted carbamate is decomposed in the stripper. (UTI) Heat Recycle Process (see Fig.2. low pressures are applied. Ammonia (containing passivating air). However.1. 17 and 18) The synthesis stage of the Stamicarbon process consists of a urea reactor (c). the licensor of these processes has announced a stripping process (the ACES process. Ammonium carbamate is formed within the coil. These low concentrations of both ammonia and carbon dioxide in the stripper efﬂuent can be obtained at relatively low temperatures of the urea solution because carbon dioxide is only sparingly soluble under such conditions. this shifts Reaction (5) to the right. In the reactor. Here. this probably means the end of the TEC MTC conventional process line. This stripping action is effected by countercurrent contact between the urea solution and fresh carbon dioxide at synthesis pressure.3. Conventional Processes As explained in Section 3. a relative high NH3 : CO2 ratio (4. Urea Technologies Inc. 3.3).12 Urea MTC (Mitsui Toatsu Corporation) Conventional Processes of Toyo Engineering Corporation.2. The continuous evolution of these processes is reﬂected in their sequential nomenclature: TR – A TR – B TR – C TR – CI TR – D Total-Recycle A Process Total-Recycle B Process Total-Recycle C Process Total-Recycle C Improved Process Total-Recycle D Process relevant in the evaporation section of the plant. The HNCO removed via the gas in the evaporators collects in the process condensate from the vacuum condensers. an NH3 : CO2 molar ratio of 3 : 1 is applied. exits the coil at the bottom. conventional processes have generally been replaced by stripping processes. where low temperatures shift Reaction (5) to the left. and then ﬂows up and around it–the exothermic heat of carbamate formation in the coil driving the endothermic dehydration of carbamate to urea outside the coil. . As a result of this mechanism of chemical entrainment. a stripper for unconverted reactants (d). The extent to which this reaction occurs is again determined by kinetics. 3. 16). see Section 3.1.3. attempts to minimize entrainment from evaporators with physical (liquid – gas) separation devices are destined to be unsuccessful.2 : 1) is applied.3.2. Partial-recycle versions of these processes were also realized. Description of Processes 3. The reactor efﬂuent is depressurized and subcooled. consequently. Only two conventional processes may still have some importance in the near future. j) is minimized. where ammonia and carbon dioxide are stripped off. low concentrations of these constituents in the liquid phase. and about 60 % of the feed CO2 are charged to the top of an open-ended coil reactor (c) operating at 210 bar. Urea as an 86 – 88 % solution is concentrated by evaporation (i) before granulation or prilling. Gases leaving the ﬁrst decomposer separator (g) are mixed with about 40 % of the feed carbon dioxide and partially condensed in the heat recovery section (i – k). These TEC MTC conventional processes were applied in more then 70 plants. and the ﬂashed gases are released before the ﬁrst decomposer (f ). Stripping Processes 3. again forming urea. such that the recycle from the low-pressure recirculation stage (h.3. Stamicarbon CO2 -Stripping Process (Figs. The conventional processes developed by Toyo Engineering Corporation (TEC) were successfully commercialized until the mid1980s. recycled carbamate. resulting in a transfer of NH3 and HNCO into the gas phase and. The reactor is claimed to achieve a uniform temperature proﬁle in this way. and a high-pressure reactor off-gas scrubber (f ).2. Low ammonia and carbon dioxide concentrations in the stripped urea solution are obtained. a high-pressure carbamate condenser (e). The two combined gas streams are then further condensed and form the carbamate recycle ﬂow. The process is applied in eight small-scale and two medium-scale plants.
i) Urea concentrator. h) Low-pressure decomposer and rectiﬁer. h) Second decomposer. Stamicarbon CO2 -stripping urea process (The process suitable for combination with a granulation plant is shown here. i) Pre-evaporator. TCW = Tempered cooling water . k) Evaporator. b) High-pressure ammonia feed pump. d) High-pressure stripper. j) Carbamate heater. combination with prilling is also possible. g) First separator. e) Liquid distributor (used as ﬁrst ﬂash vessel). g) Low-pressure absorber. l) Vacuum condensation section. c) Urea reactor with internal coil. b) Hydrogen removal reactor. f) High-pressure scrubber. c) Urea reactor. m) Process condensate treatment CW = Cooling water.Urea 13 Figure 16. UTI heat recycle urea process a) CO2 compressor. d) Air compressor. j) Low-pressure carbamate condenser. l) High-pressure carbamate recycle pump CW = Cooling water Figure 17. e) High-pressure carbamate condenser. k) Ammonia heater.) a) CO2 compressor. f ) First decomposer.
If the process is combined with a prilling tower for ﬁnal product shaping. As a result of urea and water formation in the condensing zone. suitable for. Because of the ideal ratio between ammonia and carbon dioxide in the recovered gases in this section. Only one low-pressure recirculation stage is required due to the low ammonia and carbon dioxide concentrations in the stripped urea solution. which are stripped off with steam and returned to urea synthesis via the recirculation section. additional air is supplied to the fresh carbon dioxide input stream. As a result. are purged from the synthesis section. the condensation temperature is increased.. whereas low moisture contents are economically achieved in a two-stage evaporation section. If the process is combined with a granulation unit. 0. When urea with an extremely low biuret content is required (at a maximum of 0. and no separate ammonia recycle is required. e. Apart from the air required for this purpose. the condensation of off-gas from the stripper is carried out in a prereactor. The urea solution coming from the recirculation stage contains about 75 wt % urea. cooling tower or boiler feedwater makeup. thus transforming this “wastewater” treatment into the production unit of a valuable process condensate. pure urea crystals are produced in a crystallization section.g. This extra portion of oxygen is needed to maintain a corrosion-resistant layer on the stainless steel in the synthesis section. invariably originating from an associated ammonia plant. as well as for heating the mixture to its equilibrium temperature. This heat is used for the production of 4.5-bar steam for use in the urea plant itself. Functional block diagram of the Stamicarbon CO2 -stripping urea process Condensation of ammonia and carbon dioxide gases. hydrogen is catalytically removed from the carbon dioxide feed (b). mainly oxygen and nitrogen. the heat liberated from ammonium carbamate formation is at a high temperature. Higher moisture contents can be realized in a single-stage evaporator. This process condensate treatment section can produce water with high purity. always contains hydrogen. the ﬁnal moisture content of urea from the evaporation section is ca. Before the inert gases. Further . Figure 18. The feed carbon dioxide.14 Urea washing of the off-gas is performed in a lowpressure absorber (g) to obtain a purge gas that is practically ammonia free. water dilution of the resultant ammonium carbamate is at a minimum despite the low pressure (about 4 bar).3 wt %). occurs in the highpressure carbamate condenser (e) at synthesis pressure. they are washed with carbamate solution from the lowpressure recirculation stage in the high-pressure scrubber (f ) to obtain a low ammonia concentration in the subsequently purged gas. leaving the stripper. These crystals are separated from the mother liquor by a combination of sieve bends and centrifuges and are melted prior to ﬁnal shaping in a prilling tower or granulation unit. depending on granulation requirements. Before this process condensate is purged. Since the introduction of the Stamicarbon CO2 -stripping process. some 125 units have been built according to this process all over the world. The condensation in the high-pressure carbamate condenser is not effected completely. urea is hydrolyzed into ammonia and carbon dioxide (l). Remaining gases are condensed in the reactor and provide the heat required for the dehydration of carbamate. As a result of the efﬁciency of the stripper. the ﬁnal moisture content may vary from 1 to 5 wt %. where sufﬁcient residence time for the liquid phase is provided. To avoid the formation of explosive hydrogen – oxygen mixtures in the tail gas of the plant. thus enabling the production of steam at a higher pressure level . In an improvement to this process. The process condensate emanating from water evaporation from the evaporation or crystallization sections contains ammonia and urea.25 wt %. the quantities of ammonium carbamate for recycle to the synthesis section are also minimized. This solution is concentrated in the evaporation section (k).
in this way a top product consisting of pure gaseous ammonia. The steam produced is used effectively in the back end of the process. titanium and bimetallic zirconium – stainless steel tubes have been used . some water is added to the bottom section of the column to dilute the ammonium carbamate below its crystallization point. At the tube side of this condenser the off-gas is absorbed in recycled liquid carbamate from the medium-pressure recovery section. The pure ammonia off-gas is condensed (k) and recycled to the urea synthesis section. relatively high temperatures (200 – 210 ◦ C) are required to obtain a reasonable stripping efﬁciency. The liquid ammonium carbamate – water mixture obtained in this way is also recycled to . the urea solution from the high-pressure stripper is subjected to the decomposition of carbamate and evaporation of ammonia (i).Urea 15 Figure 19. Because of this high temperature. Liquid ammonia reﬂux is applied to the top of this rectiﬁer ( j). Functional block diagram of the Snamprogetti self-stripping process 3. The off-gas from this medium-pressure decomposer is rectiﬁed. 3. through the carbamate separator (e) back to the reactor (b). typically operated at 18 bar. Later versions of the process abandoned the idea of using ammonia as stripping agent. The process uses a vertical layout in the synthesis section. an NH3 : CO2 molar feed ratio of ca. from the stripper (h) via the high-pressure carbamate condenser (f ). is maintained by using an ammonia-driven liquid – liquid ejector (c) . The heat of absorption is removed through the tubes. ammonia was used as stripping agent. so the recirculation section of the plant requires an ammonia – carbamate separation section. Off-gas from the stripper is condensed in a kettle-type boiler (f ) .3. stripping was achieved only by supply of heat (“thermal” or “self”-stripping). To prevent solidiﬁcation of ammonium carbamate in the rectiﬁer. Even without using ammonia as a stripping agent. In the medium-pressure decomposition and recirculation section. as in conventional processes (see Fig. 19).and Self-Stripping Processes [41–47] In the ﬁrst generation of NH3 . which are cooled by the production of low-pressure steam at the shell side. stainless steel is not suitable as construction material for the stripper from a corrosion point of view. Snamprogetti Ammonia. causing an ammonia overload in downstream sections of the plant. and a bottom product of liquid ammonium carbamate are obtained.  (see Fig. 20).5 is applied. Recycle within the synthesis section. . which is operated at 150 bar.2. In the reactor.and self-stripping processes. The stripper is of the falling ﬁlm type . the stripper efﬂuent contained rather large amounts of dissolved ammonia.2. Since stripping is achieved thermally. the NH3 : CO2 ratio in the stripper efﬂuent is relatively high. Because of the extreme solubility of ammonia in the urea-containing synthesis ﬂuid.
l) Ammonia receiver. h) High-pressure stripper. Functional block diagram of the ACES urea process . j) Ammonia – carbamate separation column. f) High-pressure carbamate condenser. o) Low-pressure decomposer and rectiﬁer. Typically.16 Urea Figure 20. w) Wastewater treatment. k) Ammonia condenser. q) Low-pressure carbamate receiver. Concentrating the urea – water mixture obtained from the low-pressure decomposer is performed in a single or double evaporator (s – v). The process condensate obtained from the evaporation section is subjected to a desorption – hydrolysis operation to recover the urea and ammonia contained in the process condensate. further decomposition of ammonium carbamate is achieved. In this way. b) Urea reactor. The urea solution from the medium-pressure decomposer is subjected to a second lowpressure decomposition step (o). a two-stage evaporator is required. r) Low-pressure off-gas scrubber. g) High-pressure carbamate pump. p) Low-pressure carbamate condenser. Up to now. so that a substantially carbamate-free aqueous urea solution is obtained. Off-gas from this low-pressure decomposer is condensed (p) and recycled as an aqueous ammonium carbamate solution to the synthesis section via the medium-pressure recovery section. the consumption of low-pressure steam by the process is reduced. s) First evaporation heater. In some versions of the process. e) Carbamate separator. The purge gas of the ammonia condensers is treated in a scrubber (n) prior to being purged to the atmosphere. Schematic of the Snamprogetti self-stripping process a) CO2 compressor. d) High-pressure ammonia pump. x) Vacuum condensation section CW = Cooling water the synthesis section. m) Low-pressure ammonia pump. c) Ejector. Figure 21. heat exchange is applied between the offgas from the medium-pressure decomposer and the aqueous urea solution to the evaporation sec- tion. Here. v) Second evaporation separator. depending on the requirements of the ﬁnishing section. i) Medium-pressure decomposer and rectiﬁer. about 70 plants have been designed according to the Snamprogetti ammoniaand self-stripping processes. u) Second evaporation heater. t) First evaporation separator. if prilling is chosen as the ﬁnal shaping procedure. whereas in the case of a ﬂuidized-bed granulator a single evaporation step is sufﬁcient to achieve the required ﬁnal moisture content of the urea melt. n) Ammonia scrubber.
q) Surface condensers CW = Cooling water 3. b) High-pressure ammonia pump. ammonium carbamate is decomposed and the resulting CO2 and NH3 as well as the excess NH3 are evaporated by CO2 stripping and steam heating.3. . h) Medium-pressure absorber.Urea 17 Figure 22.  The ACES (i. Its synthesis section consists of the reactor (a). m) Process condensate stripper. and a scrubber (f ) – all operated at 175 bar (see Figs. two parallel carbamate condensers (e). g) High-pressure carbamate pump. is fed to the top of the stripper.3. In the lower part of the stripper (a falling ﬁlm heater). consisting of urea. c) CO2 compressor. j) Low-pressure decomposer. d) Stripper. Heat liberated in the high-pressure carbamate condensers is used to generate low-pressure steam in one of the condensers and to heat the urea solution from the stripper after the pressure is reduced to about 19 bar in the shellside of the second carbamate condenser. f) High-pressure scrubber. n) Hydrolyzer. The gas and liquid from the carbamate condensers are recycled to the reactor by gravity ﬂow.e. This prestrip- ping in the top is said to be required to achieve effective CO2 stripping in the lower part. unconverted ammonium carbamate. Liquid ammonia is fed directly to the reactor. k) Low-pressure absorber. two units in parallel are installed. The urea solution from the stripper. where the gaseous mixture is condensed and absorbed by the carbamate solution coming from the medium-pressure recovery stage. is puriﬁed further in the subsequent . Here. Advanced Process for Cost and Energy Saving) process has been developed by Toyo Engineering Corporation. i) Medium-pressure decomposer. l) Evaporators. whereas gaseous carbon dioxide after compression is introduced into the bottom of the stripper as a stripping aid. The overhead gaseous mixture from the top of the stripper is introduced into the carbamate condensers (e). with a typical NH3 content of 12 wt %. excess ammonia. and water. stripper (d). p) Granulation section. 21 and 22). e) High-pressure carbamate condensers. o) Prilling tower. The synthesis mixture from the reactor.. ACES Process . The stripper has two functions. Schematic of the ACES process a) Urea reactor. Its upper part is equipped with trays where excess ammonia is partly separated from the stripper feed by direct countercurrent contact of the feed solution with the gas coming from the lower part of the stripper.2. The reactor is operated at 190 ◦ C and an NH3 : CO2 molar feed ratio of 4 : 1.
ammonia and carbon dioxide. before being discharged from the urea plant. k). is removed in the second high-pressure decomposer where steam heating and CO2 stripping are applied.5 ◦ C .4. high-pressure decomposer. alternatively. Water vapor formed in the ﬁnal concentrating section is condensed in surface condensers (q) to form process condensate. The ammonium nitrate solution thus formed and the urea solution from the synthesis section are mixed to yield a product solution with the desired nitrogen content (32 – 35 wt %) directly. it has not achieved great popularity so far.3.7 % for urea prill production or by a single evaporation up to 98.  The isobaric double-recycle (IDR) stripping process. In this latter category the Stamicarbon CO2 -stripping technology is especially suitable. Other Processes Urea – Ammonium Nitrate (UAN) Production. steam-heated. Such a plant designated for the production of UAN solutions is cheaper than the separate production of urea and ammonium nitrate in investment and in operating costs.3. it is normal practice to integrate the steam systems of both plants.and low-pressure decomposers (i. j). In the ﬁrst. is characterized by recycle of most of the unreacted ammonia and ammonium carbamate in two decomposers in series. Since an ammonia plant is a net heat (steam) producer and a urea plant is a net heat (steam) consumer. operating at 19 and 3 bar. because evaporation. in a production facility specially designed to produce UAN solutions. are used as liquid nitrogen fertilizers. As a result of this choice of ratio. as well as some ammonium carbamate. Part of this condensate is used as an absorbent in the recovery sections. this large quantity of free ammonia is mainly removed from the urea solution. unconverted ammonia emanating from the stripped urea solution and from the reactor offgas is neutralized with nitric acid. The IDR process or parts of the process are used in four revamps of older conventional plants. called UAN solutions. Condensation heat in the medium-pressure absorber is transferred directly to the aqueous urea solution feed in the ﬁnal concentration section. Both feedstocks required for urea production. the ACES process can also be combined with a crystallization section to produce urea with low biuret content. are usually obtained from an ammonia plant. As a result solutions with high nitrogen content can be made with solidiﬁcation temperatures below ambient temperature.3.5 % for urea granule production. Probably because of the complexity of this process. Instead of concentration via evaporation. 3. respectively. developed by Montedison. and wastewater treatment sections are not required. In a partial-recycle version of this process.18 Urea sign. Isobaric Double-Recycle Process . Mixtures of urea (mp 133 ◦ C) and ammonium nitrate (mp 169 ◦ C) with water have a eutectic point at −26. ﬁnal product shaping for both urea and ammonium nitrate. 3. Until now. both operating at the synthesis pressure. Integrated Ammonia – Urea Production. whereas the remainder is puriﬁed in the process condensate treatment section by hydrolysis and steam stripping.and medium-pressure absorbers (h. the ACES process has been used in seven urea plants.2. In this ﬁnal concentration section (l). where heat exchange between the condensing off-gas of the medium-pressure decomposition stage and the aqueous urea solution to the ﬁnal concentration section improves the overall energy consumption of the process. the reactor efﬂuent contains a relatively high amount of nonconverted ammonia. These mixtures. The highly concentrated urea solution is ﬁnally processed either through the prilling tower (o) or via the urea granulator (p). Ammonia and carbon dioxide separated from the urea solution here are recovered through stepwise absorption in the low. A high molar NH3 : CO2 ratio (4 : 1 to 5 : 1) in the reactor is applied. . UAN solutions can be made by mixing the appropriate amounts of solid urea and solid ammonium nitrate with water or. Most of the residual ammonia. the puriﬁed urea solution is concentrated further either by a two-stage evaporation up to 99. The high-pressure synthesis section is followed by two lowerpressure decomposition stages of traditional de- . Since both processes usually contain a process condensate treatment section where medium.
The present state of the art allows reduction of these losses to <0. Many new urea plants use granulation instead of prilling as the ﬁnishing technique. and dosing of nitrogen or excessive amounts of combustibles have been suggested to avoid the risks of formation of explosive gas mixtures . but less difﬁculty in controlling dust emissions is also an advantage. Ammonia remaining in the process condensate is then removed by further steam stripping (desorption).Urea volatile components are removed by steam stripping. proper measures should be taken to minimize ammonia losses. Despite the claimed reduction in both capital and raw material cost. operated in countercurrent with respect to gas and liquid ﬂow. Two techniques are known to remove these pollutants: 1) Biological treatment [61–63] 2) Chemical hydrolysis and steam stripping to remove ammonia from the condensate Biological treatment seems to have gained only slight acceptance. Efﬂuents and Efﬂuent Reduction Gaseous Efﬂuents. Several attempts for further integration of mass streams of both processes have been published [55–59]. mainly from evaporation and subsequent sublimation of urea. and as air leaking into the vacuum sections of the process.2 – 2 wt % urea. wet impingement type devices have proved successful in removing a major part of the dust from the air.2 kg of ammonia per tonne of urea produced. The method involving chemical hydrolysis and steam stripping recycles urea (in the form of ammonia) and ammonia to the synthesis section for the production of urea. followed by hydrolysis of the urea with steam at 170 – 230 ◦ C to form ammonia and carbon dioxide via ammonium carbamate. Gaseous Emissions from Process Vents. Removal of this ﬁne urea dust from the prilling tower exhaust gas is a technical chal- lenge. Because of the coarser dust and the smaller air quantities to be handled. This is realized by using conventional absorption techniques. Urea dust formed in this way is typically very ﬁne (0. the advantages of combining these sections have been explored [52–54]. Stamicarbon System. Gaseous Emissions from the Finishing Section (Prilling/Granulation). In the Stamicarbon system  ﬁrst the bulk of ammonia is removed by pre-desorption of the process condensate. The dust produced in these granulation devices (ﬂuidizedbed granulation or drum granulation) is typically much coarser than the fume-like dust produced in a prilling tower. as process air introduced for corrosion protection. and the air introduced for anticorrosion purposes. The process condensate produced from the evaporation or crystallization sections of the plant contains 3 – 8 wt % ammonia and 0. In the prilling processes. There are potentially two sources for air pollution from a urea plant: (1) gaseous ammonia emission from continuous process vents. Catalytic combustion of the hydrogen present in carbon dioxide. but also partly via a chemical mechanism: formation of ammonia and isocyanic acid in the urea melt. and (2) urea dust and ammonia emissions from the ﬁnishing section (prilling or granulation). This results basically from the much shorter contact time of liquid urea with air. evaporation of these components. 19 3. dry cyclones cannot be used. Instead. urea dust is produced. At places where these noncondensable gases are vented. Noncondensable gases enter the urea process as contaminants in the raw materials. wet scrubbers provide adequate and much simpler dust emission control for granulation units compared to the apparatus required for emission control in prilling. these highly integrated process schemes have not gained acceptance mainly because of their increased complexity. Special attention is required to avoid explosive gas mixtures originating from combustibles (hydrogen. methane) present in the carbon dioxide and ammonia feedstocks.4. Since both .5 – 2 µm). The hydrolyzer is a vertical bubble-washer column. whereas with biological treatment the urea and ammonia present in the feed to wastewater treatment are lost to urea production. The main purpose is to improve the size and strength of the product. Several chemical hydrolysis and steam-stripping systems are described below. Liquid Efﬂuents. Because of the small particle size. followed by sublimation of this ammonia – isocyanic acid mixture to form urea dust in the colder air.
making prilled product less suitable for bulk transport over long distances. for some granulation techniques. followed by ﬁnal desorption. [68–70]. Also. the hydrolyzer is built as a horizontal column with crossﬂow operation with respect to gas and liquid ﬂow. Removal of this dust is a technically difﬁcult and expensive operation. prilling has been used widely as the ﬁnal shaping technology for urea. Like the systems described above. for example. Urea and ammonia concentrations <5 ppm in the efﬂuent are claimed.4). Some systems have been proposed [52–54] in which the wastewater treatment sections of the urea and ammonia plants are combined. Since the contact time between liquid urea and air in these processes is much lower than in prilling. 3) The crushing strength and shock resistance of prills are limited. Product-Shaping Technology Prilling. which are subsequently removed by transferring them into a steamcontaining gas phase. they also remove urea by hydrolysis to ammonia and carbon dioxide. 2) Very ﬁne dust is formed in the prilling process (see Section 3. In this process. by C & I Girdler. These techniques deviate from the prilling technique in that the urea melt is sprayed on granules. UTI System. Snamprogetti System. Granulation . therefore. Toyo Engineering Corporation also offers a system of pre-desorption and hydrolysis. This distribution is performed either by showerheads or by using a rotating prilling bucket equipped with holes. In the UTI system . Other Systems. For a long time. Also. moreover. This problem can be largely overcome with appropriate techniques to improve the physical properties. and to suppress the caking tendency. larger droplets tend to be unstable. low-pressure steam as produced in the urea synthesis section can be used as stripping agent. In prilling processes. being cooled countercurrently with up-ﬂowing air. The Snamprogetti system  also includes a system of pre-desorption.1 mm. as part of its ACES and conventional urea processes. The system is claimed to achieve residual NH3 concentrations <10 ppm. it can be removed much more easily from the cooling air. both the steam required for steam stripping and the steam required to bring the process condensate to a sufﬁciently high temperature for hydrolysis must be at medium pressure. in which the hydrolysis of urea back to ammonium carbamate is carried out concurrently with the stripping of ammonia from the liquid phase. The prilling process has several drawbacks: 1) The size of the product is limited to a maximum average diameter of about 2. the pre-desorber and the desorber operate at low pressure (1 – 5 bar). however. the remaining NH3 concentration is <1 ppm. Larger-size product would require uneconomically high prilling towers. the dust formed in granulation processes is much coarser. Urea droplets solidify as they fall down the tower. The heat of solidiﬁcation is removed by cooling air or. hydrolysis. The drawbacks of prilling have initiated the development of several granulation techniques. Because of this concept. Hydrolysis is carried out at somewhat higher temperature (230 – 236 ◦ C) and pressure (33 – 37 bar) than in the Stamicarbon process. . evaporation of water. A small amount of carbon dioxide is fed to the bottom of the column. The combination of pre-desorption and countercurrent operation of the hydrolyzer ensures that the chemical equilibrium of the hydrolysis reaction does not limit the minimum achievable urea content in wastewater to concentrations <1 ppm.20 Urea forming system. such as seeding  to improve shock resistance or addition of formaldehyde to improve crushing strength. The principal difference between these systems and the aforementioned methods is that the ammonia and carbon dioxide produced are recycled to the ammonia plant re- 3. rather than to the urea synthesis section. desorption and hydrolysis take place in a single column. which gradually increase in size as the process continues.5. this process claims minimum achievable NH3 and urea concentrations <1 ppm in the liquid efﬂuent. the urea melt is distributed in the form of droplets in a prilling tower. and ﬁnal desorption with steam stripping. Drum granulation systems have been developed.
What is not commonly known. Only for the relative small market segment of foliar spray to citrus crops is a lower biuret content (max. Pan granulation processes have also been developed. Granulated product usually also has a larger diameter (2. These solutions are designated as UAN-32 to UAN-35. The solid forms are generally classiﬁed as granular or prilled products.3 %) desirable.2 wt % is considered acceptable for nearly all fertilizer applications of urea.5 mm) than prills (1.5 mm. Although the improvements brought about by granulation are beyond doubt. loss. prilled products are usually marginally cheaper than granulated product. 21 4. Disintegration can be minimized by: 1) Providing the product pouring system with a pouring height adjuster 2) Design of “product-friendly” reclaiming systems. the ﬂuidized-bed technology from Hydro Agri seems to be most successful at this time. a lower shock resistance. Urea Supergranules. Storage. urea is a favorite ingredient. Granulated product with a very large diameter (up to 15 mm) has found limited application for deep placement in wetland rice  and forest fertilization.Urea Kaltenbach – Thuring. their capabilities in this respect differ from each other to quite an extent. its content of pH-controlling trace components is important. Studies show that only 50 – 60 % of fertilizer nitrogen applied to soil is usually recovered by crop plants. however. ash-. Technical-grade urea should be without additions. Because of this. Forms Supplied. color. For liquid compound fertilizers. however. Some urea is also used directly as a feed component for cattle. and (3) absorption. and Montedison. Low-Biuret Grade. rather than being bound to narrow speciﬁcation limits. These warehouses should be designed in such a way that the product suffers little degradation. technical-grade urea at present is mostly traded as a performance product. because of the differences in handling properties. A spouted-bed technique was developed by Toyo Engineering Corporation. Because of this. However.0 – 2. More recently spoutedbed and ﬂuidized-bed granulation techniques were introduced. The majority of urea is designated as “fertilizer grade”. prilling techniques still have a place because of the lower investment and lower variable costs associated with prilling compared to granulation. The shift from bagged to bulk transport and storage of prilled and granulated urea has called for warehouse designs in which large quantities of urea can be stored in bulk. for example. Storage. For urea used to produce urea – formaldehyde resins. and a higher caking tendency than granules. Also common to all granulation techniques is that they yield products with larger diameters compared to prilling. Several attempts have been made to increase this percentage by slowing the release of fertilizer to the ground via coating or additions .5 – 2. 0. (2) disintegration.0 mm). by Norsk Hydro and the Tennessee Valley Authority (TVA). and metal content are sometimes also speciﬁed. Slow-Release Grades. Degradation may result from: (1) segregation of ﬁnes. making granules more suitable for bulk blending to produce compound fertilizers. because reclaiming the product by means of payloaders and tractor shovels invariably leads to product disintegration Caking and subsequent product disintegration at unloading are known to result from water absorption. . Segregation of ﬁnes can be avoided through uniform product spreading during pouring. It is generally used in combination with ammonium nitrate as an aqueous solution to obtain liquids containing 32 – 35 wt % nitrogen. The ﬁtness of the product for use is judged by application-speciﬁc tests. Prilled product is considered less suitable for bulk transportation because prills have lower crushing strength. A maximum biuret content up to 1. and Transportation Forms Supplied. Feed-grade urea is supplied in the form of microprills with a mean diameter of about 0. some special forms have found limited application: Technical Grade. or migration of water. Urea may be supplied either in solid form or as a liquid. All granulation processes require the addition of formaldehyde or formaldehyde-containing components. Feed Grade. Special Grades. Urea used for this purpose should be free of additions.
the force at breakage (or at 0. Thus. 46 max. Table 2. railway tanks. wt % Bulk density (loose). the force at which it is deformed by 0.4 mm. if it is not crushed. attempts to decrease water absorption through refrigeration or air conditioning. 0. A single granule is subjected to a force that is increased at a constant rate.2. Urea prills and granules are transported by bulk transport in trucks. In addition.2. wt % Product size 1. Quality Speciﬁcations and Analysis Typical quality speciﬁcations for fertilizer-grade urea are summarized in Table 2. The ammonia content is then determined by distillation and titration. The shock resistance of granules is deﬁned as the weight percentage of a sample that is not crushed when subjected to a speciﬁed shock load.. or space heating may cause the air in the warehouse to become too dry or may result in too great a temperature difference between the product and the surrounding air. ships.0 mm.22 Urea the addition of a corrosion inhibitor to the solution. Transport and storage of UAN solutions in carbon steel lines and tanks require 5. 46 max. the warehouse (especially the roof) should be airtight and thoroughly insulated.). the total N content may be determined by the Kjeldahl method or by using a method based on hydrolyzing urea with urease followed by titration of the ammonia formed.6 wt %) to the urea melt or by addition of surfactants to the solid product.6 – 4. at seaport loading and unloading facilities.. a sample of prills or granules is shot against a metal plate . wt % Crushing strength. 1 max. Alternatively. Transportation. kg/m3 Prilled product min. and pipelines. Chap.1 mm.g. dehumidiﬁcation. especially on the shock resistance of the product. bar Shock resistance. The water content is usually determined with Karl Fischer reagent (→ Gas Production.0 – 2.3 20 – 25 min. Typical product speciﬁcations for fertilizer-grade urea Speciﬁcation Nitrogen content. by polyethylene sheeting) during prolonged transport 6) Product should be spread rather then poured solely from one point to prevent dust coning due to segregation 7) Restrict the pouring height to avoid unnecessary disintegration Liquid Fertilizer Transport. Liquid fertilizers are transported by tank cars. wt % 1. e. ships. 85 90 – 95 730 95 750 – 790 Granulated product min.25 30 – 60 100 The total nitrogen content is usually determined by digesting urea with sulfuric acid toyield ammonium sulfate.3. the solid form is still the most popular by far. wt % Water content. wt % Biuret content. 1 max. Biuret is determined by the formation of a violet-colored complex of biuret with copper(II) sulfate in an alkaline medium and subsequent measurement of the absorbance of the colored solution at 546 nm. a number of “good housekeeping” rules should be adhered to: 1) Do not load or unload during rain 2) Make sure that the means of transport is clean and dry 3) Close the ship’s hold when rain is imminent 4) Do not replace the air above the product or ventilate the holds 5) Cover the product (e. To determine shock resistance. Great demands are made. The capabilities of a modern urea plant are better than the typical trade data given in this table. 8.g. Although liquid fertilizer is generally accepted as the most economic form to distribute. rail cars. Distribution of large quantities of liquid fertilizer requires a complex infrastructure and is limited at present to large farm units in developed countries. To withstand numerous and rapid loading and unloading operations.1-mm deformation) being recorded. is that excessive drying of the product during storage also leads to a higher caking tendency and that migration of water from warm product in the bulk of a pile to the cold surface leads to crust formation. 0. Crushing strength is deﬁned as the force required per unit cross-sectional area of a granule to crush the granule or. Instead. The caking tendency of urea can be reduced by addition of small amounts of formaldehyde (up to 0. however. product for bulk transport should have a high initial physical stability. etc.
Urea has the highest nitrogen content of all solid nitrogenous fertilizers. as a nutrient for ruminants (cattle feed). Urea is also used as a raw material for the production of compound fertilizers. ruminants can metabolize certain nitrogencontaining compounds.1. different economic laws have become valid in the former Soviet Union and Eastern Europe. A signiﬁcant proportion of urea production is used in the preparation of urea – formaldehyde resins. and in miscellaneous applications. Between 1994 and 1997. Because of geopolitical changes during the early 1990s.5×106 t. ahead of North America and the industrialized countries of Asia. They are also used to impregnate paper. Predictions of future developments of urea prices are therefore highly speculative. Economic Aspects The predicted growth in demand for urea until 1997 is slightly more than 3 % per year. as protein substitutes. Soil and Leaf Fertilization. In the United States this capability is exploited on a large scale. On a smaller scale. The world’s capacity utilization can thus be calculated to be ca. 1). and foams. in melamine production. 6.5 % per year. and leather. the fermenting and brewing industries. Because of the activity of microorganisms in their 7. The predicted growth in capacity up to 1997 will be around 1. causing those countries to supply to the world market large amounts of prilled urea at prices far below the cost to many producers [e. Uses Urea is used for soil and leaf fertilization (more than 90 % of the total use). the product sizes must match to prevent segregation of the products during further handling. Chap. At present. integration of the urea and melamine production processes is beneﬁcial. bringing the total urea demand in 1997 to some 89×106 t/a. urea is employed as a raw material or auxiliary in the pharmaceutical industry. Compound fertilizers may be produced by mixing in urea melts or urea solutions before shaping the compound fertilizers or by mixing solid urea prills or granules with other fertilizers (bulk blending). therefore. In the 1990s urea prices have shown large ﬂuctuations. whereas closure of old plants will result in a reduction of the installed capacity by some 2×106 t. Worldwide. 23 cud. by contrast. varnishes. In the latter case. in 1994 –1995 lows of $ 100 per tonne and highs of $ 250 per tonne have been reported. . Urea can be used for the removal of NOx from ﬂue gases. textiles. 89 %. In Western Europe. Since ammonia is formed as a coproduct in melamine production from urea (see Chap.. Feed for Cattle and other Ruminants. “foliar feed” fertilizers). and as a deicing agent for airport runways.g. This situation is not expected to last long.). For instance. urea has become the most important nitrogenous fertilizer. Most of the growth will occur in Asia. These synthetic resins are employed in the manufacture of adhesives. 4. The granulometry of the product is measured by conventional sieve techniques. resulting in a total installed capacity of some 100×106 t by 1997.). free on board (FOB) Black Sea $ 75 per tonne in 1993]. such as urea. although FOB prices at Black Sea ports will generally remain lower compared to other places. A little more than 7 % of the worldwide demand for urea is from industry. Urea is highly soluble in water and thus very suitable for use in fertilizer solutions (e. Melamine Production.. The amount of nondamaged product that remains after the test is determined. Urea is also used as a solubilizing agent for proteins and starches.Urea by means of compressed air under normalized conditions. in the manufacture of urea – formaldehyde resins. its transportation costs per tonne of nitrogen nutrient are lowest. in which Europe takes a leading role. molding powders. Urea – Formaldehyde Resins (→Amino Resins. with China and India in the lead. sales prices. and the petroleum industry. new plants will account for an increase in capacity of ca.g. nearly all melamine production is based on urea as a feedstock (→Melamine and Guanamines. Other Uses. 7. Chap. not much urea is used in cattle feed. 6.
producers are increasingly shifting production facilities (both new plants and relocations) to places where natural gas is plentiful and cheap. Table 3. and as stabilizers.and Arylureas Most simple substituted alkylureas are crystalline products. Chap. Alkylated and arylated ureas are used in the production of plant protection agents.6 (1H. Uninterrupted operating periods of more than one year are often achieved. H2 NCONHCONHCONH2 .4. the most important of which are listed in Table 3. and cyanuric acid. 1.and tetraethylurea and some cyclic ureas are liquids.24 Urea To cope with tough competition on the world market. Tetramethyl. as plasticizers. mp 193 ◦ C. 4.6triamine (2) is produced industrially from urea  (→Melamine and Guanamines. H2 NCONHCONH2 . is produced by heating urea in inert hydrocarbons at 110 –125 ◦ C or in the melt at 127 ◦ C . The investment costs (in 106 $) for a present state-of-the-art total-recycle urea plant are estimated to be: 1000-t/d plant (single line) 43 1500-t/d plant (single line) 52 2000-t/d plant (single line) 62 Melamine [108-78-1].4. Alkyl. 1. diimidotricarbonic diamide.3H. imidodicarbonic diamide.2. triuret. Urea Derivatives Barbituric acids and →Hypnotics. is formed on heating urea in the presence of zinc chloride. in which operating reliability is of extreme importance.3. sulfuryl chloride. .5-triazine-2. is produced by decomposing urea in a thin ﬁlm at 120 – 125 ◦ C . . Biuret [108-19-0]. and in a special process.5H )-trione (1). melamine is produced. ureas substituted at one or both nitrogen atoms and cyclic ureas Urea and tertiary alcohols ureas substituted at one nitrogen atom Phosgene and amines ureas substituted at one nitrogen atom Isocyanates and NH3 or amines ureas substituted at one or both nitrogen atoms Carbamoyl chloride and NH3 or ureas substituted at one or both amines nitrogen atoms ureas substituted at one or both Esters of carbonic or carbamic acids nitrogen atoms Urea and aldehydes or ketones ureas substituted at one or both nitrogen atoms and cyclic ureas 8. Europe seems to have lost its competitive edge in export markets due to its expensive feedstocks. Furthermore.3. mp 231 ◦ C. 5.5-triazine2. derivatives. in pharmaceutical and dye chemistry. 8. Thermal Condensation Products of Urea Thermolysis of urea gives biuret.1. or chlorosulfuric acid . Transamidation of Urea with Amines The transamidation of urea with amines is one of the most important industrial production processes for substituted ureas. Cyanuric acid [108-80-5].1. see 8. Alkylureas and polyalkyleneureas are used as additives in the production of aminoplastics.). It is also obtained by treating 2 mol of urea with 1 mol of phosgene in toluene at 70 – 80 ◦ C . Triuret [556-99-0]. Chap. Production processes for substituted ureas Starting materials Urea and amines Product 8. producers have the tendency to build plants with very high single line capacities (2000 t/d or more).2.1. Monosubstituted . Various processes can be used for the production of substituted ureas.
mp 186 ◦ C 8. .N -Diphenylurea [102-07-8]. Symmetric N.Urea ureas are produced by condensation of urea with a sufﬁciently basic amine in a 1 : 1 molar ratio in the melt at 130 – 150 ◦ C . with elimination of ammonia . 2-Imidazolidinone [120-93-4]. H2 NCONH – CH2 CH2 CH2 – HNCONH2 . Monomethylurea [598-50-5]. mp 215 ◦ C Dipropylenetriurea. mp 147 ◦ C. mp 182 ◦ C. . . 2 mol of concentrated sulfuric acid at 20 – 25 ◦ C with ice cooling [92–94]. mp 102 ◦ C. CH3 NHCONH2 . is used for the synthesis of caffeine by the Traube method and for the production of formaldehyde-free easycare ﬁnishing agents for textiles . tri-. Polyalkyleneureas can be obtained by treating di-. H2 NCONH – CH2 CH(OH) – CH2 – HNCONH2 . (CH3 )3 CHNCONH2 . Alkylation of Urea with Tertiary Alcohols 25 Diethylenetriurea.3-Propylenediurea. H2 NCONH – CH2 CH2 – HNCONH2 . are produced industrially in the melt above 180 ◦ C.2. Examples of polyalkyleneureas include the following: 1. can be produced by heating an aqueous solution of aniline hydrochloride and urea to its boiling point . Hexamethylenediurea [2188-09-2].N -dimethylurea [96-31-1]. H2 NCONH(CH2 )6 NHCONH2 . by condensation of 1. and tetraalkylenamines in concentrated aqueous solution with urea at ca. 5-hydroxypropyleneurea (5). amine salts can also be reacted with urea in the melt or by prolonged boiling in aqueous solution . Urea can be alkylated with tertiary alcohols in the presence of sulfuric acid . CH3 HNCONHCH3 . ethyleneurea (3).3. preferably at 200 – 230 ◦ C. N. C6 H5 HNCONHC6 H5 .3-propylenediamine with urea and elimination of ammonia.2. H2 NCONH – (CH2 )3 – N(CONH2 ) – (CH2 )3 – HNCONH2 2-Hydroxypropylene-1. mp 238 ◦ C. In some cases. mp 260 – 265 ◦ C . Symmetrically disubstituted ureas can be produced from 2 mol of amine and 1 mol of urea at 140 – 170 ◦ C . is produced industrially by passing monomethylamine into a urea melt . 110 ◦ C. They are used. Phenylurea [64-10-8]. 2-oxohexahydropyrimidine [65405-39-2]. Instead of the amines. Monomethylurea is used for the synthesis of theobromine. mp 147 ◦ C Cycloalkyleneureas. Phosgenation of Amines Symmetrically disubstituted ureas are produced in good yields by passing phosgene into solutions of amines in aromatic hydrocarbons . is produced by treating urea with 2 mol of tert-butanol in the presence of ca. tert-Butylurea. 8. aqueous solutions or suspensions of amines can also be reacted with . for example. H2 NCONH – CH2 CH2 – N(CONH2 ) – CH2 CH2 – HNCONH2 . carbanilide.N -dihydroxymethyl compounds for easycare ﬁnishes for cellulose-containing textiles . C6 H5 HNCONH2 . mp 131 ◦ C . propyleneurea (4).3-diurea. mp 105 ◦ C. to modify melamine – formaldehyde impregnating resins and binders for derived timber products.2-Ethylenediurea. is obtained by heating a mixture of hexamethylenediamine with an excess of urea at 130 – 140 ◦ C. mp 198 ◦ C 1. can be produced in high yields by heating 2 mol of aniline with 1 mol of urea in glacial acetic acid . and 2-oxo-5-hydroxyhexahydropyrimidine. These cycloalkyleneureas are used in the form of their N.2. .2-ethylenediamine or 1.
6. This production . mp 189 ◦ C.  is obtained in quantitative yield by heating diphenylcarbamoyl chloride with diphenylamine. is obtained by treating phosgene with monomethylaniline and sodium hydroxide. Asymmetric Diphenylurea.5. phosgene. This process is particularly suitable for the production of unsymmetrically substituted ureas . Symmetric dialkyldiarylureas are used under the name Centralite as plasticizers and stabilizers for nitrocellulose and propellants .26 Urea method can be applied to aminosulfonic and aminocarboxylic acids. R – NH2 · HX + KNCO + H2 O → R – HNCONH2 + KX + OH− Ammonia and primary or secondary amines react with carbamoyl chlorides to give the corresponding urea derivatives in good yields . mp 121 – 127 ◦ C. the corresponding substituted ureas are obtained in almost quantitative yield [104–106]. (CH3 )2 NCON(CH3 )2 . 8. Aminolysis of Esters of Carbonic and Carbamic Acids Esters of carbonic and carbamic acids (carbonates and carbamates) react with amines at ele- 4-Ethoxyphenylurea [150-69-6] (dulcin) is produced from potassium cyanate and pphenetidine hydrochloride in aqueous solution at room temperature . from which the sulfonylureas are obtained by acidiﬁcation : phosgenes . (C6 H5 )2 NCON(C6 H5 )2 . and ammonia: COCl2 + (C6 H5 )2 NH + 3 NH3 → (C6 H5 )2 NCONH2 + 2 NH4 Cl 8. .5 ◦ C.2. : Symmetric dimethyldiphenylurea. For the production of substantive dyes.7.2. (C6 H5 )2 NCONH2 . aminosulfone or aminocarboxylic acid groups are bonded by means of phosgenation  2 RNH2 + COCl2 → RNH – CO – NHR + 2 HCl Tetramethylurea [632-22-4].2. is produced from dimethylamine and phosgene and is used as an aprotic solvent . whereby the betainelike salts formed by these acids react with potassium cyanate to give ureas that are substituted at only one NH2 group . Reaction with Isocyanates Symmetrically disubstituted ureas can also be produced from isocyanates by prolonged heating in aqueous solution . Acylation of Ammonia or Amines with Carbamoyl Chlorides 8. . is produced from diphenylamine.4. Tetraphenylurea. Sulfonamides react with potassium cyanate to give potassium salts of the corresponding sulfonylureas. When ammonia or primary or secondary amines are reacted with isocyanates. Reaction of Amines with Cyanates (Salts) The salts of aliphatic or aromatic amines react with potassium cyanate at 20 – 60 ◦ C to give substituted ureas in high yields .2. The phosgenation of mixed aliphatic – aromatic amines is carried out industrially in the presence of sodium hydroxide at 40 – 60 ◦ C . bp 156. 8.
. Urea is added with cooling.and N. monoalkylureas.  is produced industrially by charging 2 mol of formaldehyde per mole of urea to a stirred vessel. Urea can bond with up to 4 mol of formaldehyde.3. and cyclic ureas generally gives unstable α-hydroxyalkyl compounds. . After a few hours the reaction mixture is cooled to room temperature and dihydroxymethylurea crystallizes out. 27 8. Hydroxymethyl derivatives of urea and cyclic ureas (9)–(15) are used in easy-care ﬁnishes for textiles . However. and cyclic ureas. for example.3.1.5oxadiazine (7) .3. in the synthesis of trimethoxymethylurea (6).Urea vated temperatures to give symmetrically disubstituted ureas [109–112]. Electron-withdrawing and electron-donating substituents next to the αhydroxyalkyl group affect the stability of these compounds and also their ability to undergo condensations.and tetrahydroxymethylureas are formed only as nonisolable intermediates.3. The addition of higher aldehydes to urea.and symmetrically disubstituted ureas. N. and the temperature must not exceed 40 ◦ C in this slightly exothermic reaction. whereas the corresponding salts of N-hydroxymethyl (17) and N-α-hydroxyethyl compounds (18) are . The solution is neutralized with triethanolamine. Tri.N -dihydroxymethylurea can be isolated in pure form .5triazines (8) [137–140].or base-catalyzed additions that are generally equilibrium reactions [113–130]. . and N. HOCH2 HNCONHCH2 OH . Reaction of Urea and Its Derivatives with Aldehydes 8. mono. the chloral – urea derivatives (16) exhibit considerable differences in reactivity compared with the N-hydroxymethyl (17) and N-α-hydroxyethyl compounds (18).N dialkoxymethyl-4-oxomethyltetrahydro-1. For example. Chloral compounds (16) can form alkali-metal salts. These differences are exempliﬁed by a decrease in the H-acidity of the OH groups . It involves acid. only monohydroxymethyl. .N -Dihydroxymethylurea [140-95-4]. α-Hydroxyalkylureas The industrial production of α-hydroxyalkylureas is limited to the addition of formaldehyde or glyoxal to urea. Hydroxymethyl derivatives of cyclic ureas can be produced by reaction of these substances with formaldehyde in an alkaline medium . The product is dried in a spray-drying tower. N.N -dihydroxymethyl-2-oxo-5-alkyltetrahydro-1. symmetrical dialkylureas.
. The process is carried out in a reactor equipped with an adequately dimensioned heat exchanger.5-dihydroxy-2oxoimidazolidine (19) in weakly acidic to weakly alkaline aqueous solution or. Condensation of chloral compounds with nucleophiles is possible only under extreme reaction conditions. whereby the equilibrium position must be adjusted by variation of the concentration and the molar ratios .5-dihydroxyimidazolidines are formed by cyclization of urea. ureidomethylation of alcohols is better at room temperature in the presence of strong acids. Sometimes. α-Alkoxyalkylureas Condensation of N-hydroxymethylureas with alcohols to give N-alkoxymethylureas (ureidoalkylation of alcohols) is of great industrial importance. The 4-hydroxycycloalkyleneureas (cyclic N-hemiacetals).N -Dihydroxymethyl-2-oxo-4. . a vacuum pump. the highly polar N-hydroxymethyl groups obtained in the initial reaction between urea and formaldehyde are acetalized with alcohols. mainly butanol and isobutanol. a wide range of aminoplastic resins for coatings exist that are readily soluble in common paint solvents. by direct reaction of urea with glyoxal and formaldehyde in the appropriate molar ratio in weakly acidic to neutral solution at 40 – 80 ◦ C. Some 4-hydroxycycloalkyleneureas are so reactive that they can be converted into the N-αalkoxy compounds (21). Pure hydroxymethylureas and an excess of alcohol are reacted in the presence of catalytic amounts of acid. However.4). a distillation column. which are becoming increasingly important for environmental reasons. The alcohol-modiﬁed urea – formaldehyde condensation products are used as resins for heat. which are obtained by treating suitable aldehydes with ureas. N-α-hydroxyethyl compounds can be converted smoothly with alcohol into N-α-alkoxyethyl compounds in basic and sometimes even in neutral media. and the formation of byproducts and polycondensation products. The molar ratios vary between 2 and 4 mol of formaldehyde and 2 and 5 mol of alcohol per mole of urea. its stability to hydrolysis. sometimes in the presence of catalytically active buffers . For example. more elegantly. To convert urea – formaldehyde resins to resins that are soluble in organic solvents. with glyoxal [143–145]: N.5-dihydroxyimidazolidine (20) is produced by hydroxymethylation of 4.or symmetrically disubstituted derivatives.28 Urea 8. . as well as ethanol and methanol or their mixtures.2. These compounds can be produced industrially by cyclocondensation of urea with active enolizable aldehydes (see Section 8. The reactivity of N-hydroxymethyl compounds lies between that of the chloral and Nα-hydroxyethyl compounds. Besides the watersoluble or almost solvent-free resins.3. a water separator. The alcohol-modiﬁed urea – formaldehyde resins are produced industrially by passing aliphatic alcohols into aqueous solutions of urea and formaldehyde or solutions of hydroxymethylated ureas in the presence of small quantities of acid at 90 – 100 ◦ C so that the water formed and excess alcohol distill off.or acid-curing coatings. and for alcohols that are sparingly soluble in water. or its mono. Compound 20 and its derivative in which the OH groups are partly acetalized with methanol are used as formaldehyde-free cross-linking agents for easy-care ﬁnishes for cellulose-containing textiles. At elevated temperature the reaction can be carried out under weakly acidic conditions. 2-Oxo-4-hydroxyhexahydropyrimidines also belong to the group of α-hydroxyalkylureas. are stable. 2-oxo-4. The nature and quantity of the acid catalyst depend on the reactivity of the N-hydroxymethyl compound. (22) even in a neutral medium by heating with alcohol : unknown.3.
In industrial production processes an aprotic entrainer (e.3. Isobutylidenediurea (24).5(1H. The aldehyde group ﬁrst adds to the urea to form an α-hydroxyalkylurea. α.Urea 29 To shift the equilibrium in the N-αureidoalkylation of alcohols in the direction of the N-α-alkoxyalkyl compounds. which is sparingly soluble in water. which then reacts with a second molecule of urea or with another α-hydroxyalkylurea to give linear or branched α. : Reaction of equimolar quantities of urea and formaldehyde in acidic solution gives polymethyleneureas as a result of stepwise ureidomethylations: Kadowaki obtained polymethyleneureas containing up to ﬁve urea groups joined by methylene bridges by means of a stepwise synthesis .3H )-dione (23) has achieved importance as a polymerizable coating component .3. In the ureidomethylation of alcohols that are immiscible or sparingly miscible with water. Because of their extreme insolubility.. Polymerizable compounds are obtained by ureidoalkylation of unsaturated alcohols (e.α -alkyleneureas: Isobutylidenediurea is also a slow-release nitrogen fertilizer used in various special fertil- . for example. Higher-boiling alcohols can also be ureidomethylated by transacetalization of the N-methoxymethyl compounds. Tetraallyloxymethyltetrahydroimidazo[4. an aromatic) is used.α -Alkyleneureas α.g.5-d]imidazole2. no higher polymethyleneureas have yet been isolated.. the water formed during the reaction must be removed. Polymethyleneureas are used as slowrelease nitrogen fertilizers. allyl alcohol . is obtained by condensation of urea with isobutyraldehyde in a molar ratio of 2 : 1 in a weakly acidic medium: 8. ).g. an excess of alcohol is used and water is removed by azeotropic distillation.α -Alkyleneureas are obtained by condensation of urea or its derivatives with aldehydes in a weakly acidic medium.
4-Oxo-3. The product is dried by using plate driers and processed by sieving.or 4. and grinding. . isobutyraldehyde.3. Isobutylidenediurea is produced by a continuous process. or eight ring atoms. 4. by means of a double α-ureidoalkylation with urea: .3. and spiro compounds can be produced this way . Saturated and unsaturated cyclic ureas with ﬁve.5-Dihydroxy.3. cyclocondensation occurs . : izer formulations. These compounds are obtained by cyclizing ureidomethylation of urea with formaldehyde and a primary amine [137–140]. 8. : Industrially important reactions are those of urea with formaldehyde.5oxadiazines (25) occurs . Treatment of urea with formaldehyde in a molar ratio of 1 : ≥4 Bicyclic Ureas.5(1H. . These compounds can be obtained directly by condensation of urea with formaldehyde and alcohols . seven.or 1.5-dialkoxymethyltetrahydro1. six.3. The hydroxymethyl and methoxymethyl derivatives of 2-oxo-5-alkylhexahydro-1.5-oxadiazines are used as cross-linking agents for easy-care ﬁnishing of textiles. acetaldehyde. and their mixtures.3H )dione (26).4.3-position). urea is charged continuously with a screw feed via a belt weigher and is reacted with a stoichiometric quantity of isobutyraldehyde in the presence of semiconcentrated sulfuric acid in a mixer.30 Urea gives an equilibrium mixture of hydroxymethyl derivatives.5triazines have achieved importance as crosslinking agents for easy-care ﬁnishing of cellulose-containing fabrics. According to a patent published by Mitsubishi Chemical Industries . such as tetrahydroimidazo[4.5-d]-imidazole-2. If the urea bears a nucleophilic substituent on the second nitrogen atom.2. On ureidomethylation of a hydroxymethyl group bonded to the second nitrogen atom of the urea. .5dialkoxyimidazolidin-2-ones can be converted into bicyclic ureas. cyclocondensation to hydroxymethylated 4-oxotetrahydro-1. In the last section of the mixer the reaction product is neutralized by injecting dilute aqueous potassium hydroxide solution.or a vinylogous ureidoalkylation [113–115]. bicyclic and polycyclic heterocycles (with both uncondensed rings and rings anellated in the 1. Cyclic Urea – Aldehyde Condensation Products Almost all cyclizations of urea and its derivatives with aldehydes involve an α. ﬁltering.
which have at least one activated hydrogen in α-position to the carbonyl group. . 2-oxo-4-alkoxyhexahydropyrimidines (30) are formed . 2oxo-4-hydroxyhexahydropyrimidines (29) are formed in the presence of an acid . i. . aliphatic and aromatic aldehydes generally react only as carbonyl components in reactions with urea and its derivatives. 10 mol isobutyraldehyde is added with stirring. The tetrachloro compound (27) is used as a chlorine-transfer agent for mild chlorination reactions and as a bleaching agent for textiles [159–161]. A solution of urea is acidiﬁed to pH <3 with sulfuric acid. giving linear or branched condensation products. 1 mol of aldehyde as the carbonyl component. The precipitated product is neutralized by decantation and stirring with water. Symmetrical di-α-hydroxyalkyl compounds (28) and poly-α-alkyleneureas are formed as intermediates. a bond is formed between the nucleophilic α-carbon atom of one αhydroxyalkyl group and the carbon α to the urea nitrogen in the second α-hydroxyalkyl group to give 2-oxo-4-hydroxyhexahydropyrimidines (29). and a 40 % glyoxal solution is added slowly. At the end of the reaction the molar ratio of glyoxal to urea is adjusted to at least 1 : 2. After being heated at 85 ◦ C for 2 h. can be obtained directly by condensation of glyoxal with excess urea in an acidic medium . In the form of its tetrahydroxymethyl derivative (15) the product has achieved importance as a cross-linking agent in easy-care textile ﬁnishes . Then. . Reaction temperature should not exceed 70 ◦ C. If these cyclocondensations are carried out in the presence of alcohols. the product is ﬁltered and washed with water. Under mild conditions (i.e.5(1H.5. These cyclocondensations can also be carried out between urea and two different aldehydes. In cyclocondensation. Preparation of 2-Oxo-4-hydroxy-5. They all contain the groups necessary for cyclocondensation involving an α-ureidoalkylation.5-d]imidazole2. . . (see right column) In the cyclocondensation of urea or its monoor symmetrically disubstituted derivatives with aldehydes.5-dimethylhexahydropyrimidine (31)  . acetylenediurea (26). an α-ureidoalkylation at nucleophilic α-carbon atom in the aldehyde occurs.Urea 31 Tetrahydroimidazo[4. The synthetic possibilities for cyclizing αureidoalkylations with compounds containing enolizable carbonyl groups are manifold. For example. at least one of which must have an enolizable carbonyl group. 3H )-dione [496-46-8]. In a more strongly acidic medium and at elevated temperature...5dimethyl-6-isopropylhexahydropyrimidine (mp 220 –222 ◦ C). and the second mole of aldehyde as the nucleophilic component with activated α-hydrogen. however. the cyclocondensation of 1 mol of urea with 1 mol of formaldehyde and 1 mol of isobutyraldehyde in the presence of an acid gives 2-oxo-4-hydroxy5. Aldehydes and ketones are particularly important because they react not only as nucleophiles but also as carbonyl components in these cyclocondensations. The saturated and unsaturated Nalkoxymethyl compounds (23) are used as crosslinking agents in the paint and coating industry. One liter of a 30 % aqueous urea solution (5 mol) is treated with 100 mL of 50 % sulfuric acid in a stirred tank reactor with reﬂux cooling. in weakly acidic media).e. the NH component.
Preparation of N. Chem.and linear condensations.7-Dioxo-4. . 2-Oxo-4-ureido-6-methylhexahydropyrimidine is used as a slow-release nitrogen fertilizer . crotonylenediurea (33). The exothermic reaction is kept at 38 – 60 ◦ C by controlled cooling. and isobutyraldehyde in acid-catalyzed cyclo. . which are not or only mono-substituented in the 5-position. Average residence time in the cascade is 40 min. Isobutyraldehyde is added in the presence of a strong mineral acid to bring about cyclocondensation.5-dialkylhexahydropyrimidines are used in the form of their N. 2-Oxo-4-ureido-6-methylhexahydropyrimidine is produced industrially in a continuous process employing a stirred tank cascade. Basaroff. Chem.N -bisneopentals can be produced from urea. is obtained either by condensation of urea with crotonaldehyde in the presence of acid  or by the industrially more straightforward route involving condensation of urea with acetaldehyde in the molar ratio 1 : 1 in the presence of acid . 2 (1870) no. . whose OH groups can undergo nucleophilic substitutions similar to those undergone by Nhydroxymethylureas. the reaction mixture is neutralized with aqueous potassium hydroxide solution. Phys. References 1. o 253 – 256. A. formaldehyde. 283. Urea is treated with formaldehyde in the molar ratio 1 : 1 at pH >9 and 50 – 60 ◦ C in the presence of an excess of methanol.5-dimethylhexahydropyrimidine.N -Dihydroxymethyl-2oxo-4-hydroxy(methoxy)-5. The pH is initially kept above 3 and in the ﬁnal reactors below 2 by addition of sulfuric acid. and hydroxymethylation is carried out with formaldehyde. 2. It decomposes as a result of acid hydrolysis induced by humic acids during the growth period of plants. A 70 % urea solution is treated with acetaldehyde at a molar ratio of 1 : 1 in the presence of a catalytic quantity of 75 % sulfuric acid. bringing about mineralization of the nitrogen it contains. 12.5-dimethylhexahydropyrimidyl-N.5-dimethylhexahydropyrimidines are cyclic N-hemiacetals. W¨ hler. 2 (1828) no. 2-Oxo-4-hydroxy-5. Ann. 9. depending on the molar ratios of the starting materials . Prakt. This fertilizer is characterized by its extreme insolubility in water and is therefore not washed out of the soil by rain or irrigation. I. These bisneopentals react further according to a Claisen – Tishchenko reaction to give soft and hard resins with good light stability for the paint and coatings industry. .5-d]pyrimidine is formed as a byproduct in the second route [168– 170]. 1. 2-Oxo-4-hydroxyhexahydropyrimidines (32). react with ureas to give 2-oxo4-ureidohexahydropyrimidines (32). 2-Oxo-4-hydroxy.N -dihydroxymethyl compounds in noncrease ﬁnishes for cellulose-containing textiles .and 2-oxo-4-alkoxy-5. The reaction mixture is rendered alkaline. 2-Oxo-4-ureido-6-methylhexahydropyrimidine [1129-42-6]. 2.5-dimethyldecahydropyrimido[4. Drying is carried out in a spray tower. J. In the last stirred tank.32 Urea The 2-oxo-4-hydroxy-5. F.
Barake. Lagana). 2. 22 (1972) 727 – 737. E. 45.– Dec. Schmid. 80 (1984) no. A. ed. 7. U. 18. Inoue et al. 13. pp. Eng. 45 (1972) no. US 4 327 068. K. M. Prikl. 143 – 144. 3rd ed. G. US 4 301 299. 1975 (M. 10. Hydrocarbon Process. 1616 – 1619 (Part II). 3. Eur. Ostrogovich.). M. Chem. 5. 4. 2. 31 – 35. Kanai. D. Kinno. S. Prikl. 3rd. 46. L. 1992 (V. 1980 (G. Zardi). Bacaloglu. Ostrogovich. F. Seidell: Solubilities of Organic Compounds. M. Montedison. 409 – 410 ( Zh. Suppl. Chem. A. 22 – 29. 393. News. Khim. Unie van Kunstmestfabrieken. 314 – 322. D. 3. F. D. Zardi). Snamprogetti. C. 2. Kirk-Othmer. Gorlovskii. (Leipzig) 32 (1980) no. M. Eng. The Chem. J. P. GB 1 581 505. Guadalupi.. G. Khim. S. J. D. 3rd ed. van den Berg. Kucheryavyi. 1st Dec. Eng. M. 22 – 35. Egan. 777 – 780. 36. 11. J. Miola. Lemkowitz. Inoue. Kaasenbrood. Schubert. (Leningrad) 42 (1969) no. X.. 31. US 3 720 548. C. Khim. et al. Seidell. Toyo Engineering Corp. J. 1983 (S. 28 (1936) no. 1987 (J. US 3 876 696. 33. 517 – 522. ( Zh. 45 (1972) no. Technol. 6. ( Zh. Linke: Solubilities of Inorganic and Organic Compounds. Zuidam. G. E. 11. Roum. (Leningrad) 54 (1981) no. J. Faita.). A. 36 (1991) no. New York 1952. J. Pagani. 2548 – 2551). J. 8. 32. 16. H.. 9 (1982) 15 – 16. P. A. Chem. Epperly. Chermin. Stamicarbon. Vogel. 44. J. Eng. Chem. F. 33 24. 1955 (J. U. Soc. 440 – 469. Jonckers). B. M. 1977. Hydrocarbon Process. Chem. R. W.. Rev. Meessen. New York 1941. 6. Kucheryavyi. Chem. Midgley. Res. GB 2 109 372. ed. 21. Linke: Solubilities of Inorganic and Organic Compounds. 9. Grassini). ( Zh. Seidell.. EP 0 155 735. 41. Kozyro. Prog. I. Chem. (Paris) 60 (1948) no. 1339 – 1345 (Part I). . G. Inoue. Biotechnol. Skotnikova. Van Nostrand Co. 20. R. Jpn. Age India 26 (1975) no.. W. Zardi. B. 1. 29. Sipkema). S. Bull. V. Ind. P. Nitrogen 185 (1990) May – June. A. 10. 1990 (S. A. 39. Lagana. R. 17. 26. Data 11 (1966) no. Ortu. Ind. 2. vol. V. 7.). C. Berliner. 856 – 866. 2. Lasalle. Rev. A. 264 – 288. US 3 954 861. New York 1952. (Leningrad) 46 (1973) no. Jpn. Lagana). paper presented to The Fertilizer Society of London. 49. Menicatti. GB 2 109 372. Frejacques. 42 (1969) no. Krasulin. Ya. 12. Chem. Krasulin. (Leningrad) 60 (1987) no. H. Chimia 34 (1980) no. 35. Appl. 49 (1970) no. Ind. 47. 249 – 260. A. (Heidelberg) 21 (1991) no. Appl. Chem. 1982 (V. De Jonge. ( Zh. T. Nitrogen 194 (1991) Nov. A. I. Toyo Engineering Corp. Appl. M. p. Tech. (Leningrad) (1987) no. U. Snamprogetti. 3rd. US 4 899 813. Chim. Durisch. V. 4. Snamprogetti. 46 (1973) no. 1981 (S. 104 – 108). 51. 28. Elkanzi. H. Ono). 407 – 409. C. 43 (1992) 396 – 401. (1977) Dec. 254 – 259 (Eng. Aug. Roum. 393 – 396). 25. N. A. 27. (Leningrad) 59 (1986) no. G. 7. Chem. Appl. J. 1985 (G. J. 4.). P. Snamprogetti. 115 – 116 (Eng. Stamicarbon. J. Fert. Pagani).). Pagani).). C. Miola. L. Barake. 1353 – 1355. P. Granelli). Srivastava. W. Lagana. 1983 (G. C. Otsuka. 54 (1975) no. 1456 – 1459. E. 32 – 38. R. C. Chem. vol. 1. 1976 (M. G. Soc. W. 19. 52. Montedison. Snamprogetti. Montedison. Ind. Banerjee. GB 1 542 371. M. 5. Dooyeweerd. Bull. A. Urea Casale. J. 1983 (S. 4.. H. 2. Appl. F. Van Nostrand. 31 (1992) no. P. 1985 (K. 10 (1965) 1111 – 1123. Meessen. Logemann. Stamicarbon. 15. 1973 (F. 192 – 194. Tech. 7. Inoue et al. U. EP 0 504 621. 53 (1980) no. J. 3 – 4. Richter. G. Res. 10 (1965) 1125 – 1135. 23. 1. Prikl. 102 – 104 (Eng. Chem. 429 – 431. EP 0 132 194. Van Nostrand Company. EP 0 212 744. G. 1978. V. P. EP 0 096 151. 37. Chem. 43. US 2 727 069. J. R.. Chim. Chem. van Waes). Werkst. 50. Eng. Korros. U. B. Guadalupi. 1898 – 1901. Zinov’ev. 4.. 42. Uchino. 40. 34. Chem. 22. van den Berg. Prikl. Khim. K. Fukui. E. 5. M. J. Prikl. R. P. Chim. 7. 38. Appl. 96 – 99. GB 1 506 129. Kabo. Snamprogetti. Logemann). Dalidovich. H. 30. I. 7. 16 (1979) nos. Jojima. Spasskaya. V. 446 – 447). Luff. K. A. 1979 (U. B. Zardi. S.. 48.. Khim. X. Kozyro. Chem. Bacaloglu. Nitrogen 143 (1983) May – June. 22 – 28. 2. G.Urea 3. H. Lemkowitz. (Leningrad) 59 (1986) no. Zardi). F. Toyo Engineering Corporation. 14. Suppl. Dijkhuis.
J. Ber. Berlinerblau. GB 1 520 561. Michler. 31 – 36. O. III. 9 (1989) no. L¨ ttringhaus. 1906. Chem. H¨ chst. 455 – 494. Chem. 94. A. 1888. Hebd. Saviano). Dtsch. A. V. 72 (1950) 3205. 68 (1848) 325. F. a Bayer. Friedl¨ nder 9. Chem. H. Wurtz. DE 116 200. Synth. vol. Ber. Int. Houben-Weyl. Justus Liebigs Ann. Madison 1971. 2.34 Urea 81. 2. B. US 5 223 238. EP 0 037 148. VIII. 105. J. 37 – 39. Chem. C. Chem. Biotechnol. . DE 896 640. Chem. T. Nitrogen 95 (1975) May/June. 103. B. 76. R. T. G. Fert. 78. 4 (1927) 138. Prog. Arnold). N. Technol. Friedl¨ nder 9. Ges. 153. Sulfphur’s 12th Int. W. 1981 (V. Unie van Kunstmestfabrieken. Willems. Keller. March 27 – 29. J. Marcel Dekker. Reynolds. 29 (1949) 18. 27 (1883) no. 61. 1943 (C. 40 (1946) 1876. a Bayer. H. 69. 1926. Mavrovic: “Pollution Control in Urea Plants. 87. DE 689 421. IG Farbenind. Chem. 93. 1988. Wurtz. Ind. 1982 (J. Fert. Org. Prot. Saviano). Kellogg Co. Unie van Kunstmestfabrieken. Smith. Chem. K. Justus Liebigs Ann. W. 91. 1927 (T. 95. 1983 (P. 65. 82. 2. 74. 1980 (V.” Part A. Blanchard. US 4 235 816. 55 (1992) no. Dtsch. Pagani). u Int. Ali. Petersen: “Chemical Processing of Fibers and Fabrics. 15. A. M. 90. a Bayer. The M. Snamprogetti. Hauck. 101. Emeron.” Br. Knoll. 291 (1896) 374. Rev. Klok). 47 (1914) 2440. 71. P. 58. III. 200. J. Haworth. Kr¨ nzlein. Ber. Czup-pon). Sci. 8. 711. W. Chem. I. S. Khim. (N. GB 2 060 614. 89. 77. Lagana. O. Unie van Kunstmestfabrieken. Lagana. V. 9 (1876) 995. 54. C. Ges. Diamond. A. 191 – 199. Am. Hofmann. Eng. 98. 84. M. Soil Science Society of America. H. 27 (1848) 242. Snamprogetti. Sonn. R. Zh. 968. C. DE 46 737. Du Pont. DE 131 513. 57. Org. G. US 2 760 961. Chem. 450. Wurtz. Chem.): Handbook of Fiber science and Technology. A. L.. R. 13. Chem. Eng. Abstr. M. Chem. S. 56. 104. 1943. Synth. A. T. Chem. 63. J. Jonckers). 2nd ed. Chem. Chem. US 2 145 242. 1. 59. Schiff. Snamprogetti. EP 0 053 410. o a 395. III (1955) 151. Justus Liebigs Ann. News (1992) May. 1981 (M. A. Dtsch. G. 1899. 60. 83. Henke). W. 9 (1876) 396. 372. Nitrogen 88. G. 12 (1879) 1162. 1991 (F. J. Ed. 56 (1956) 95 – 197. A. Chem. K. 108. 164. Prikl. J. Snamprogetti. F. 66. CIOS. C. Cavallanti). Chem. H. W. Craswell. Fert. 92. 79. Chem. Friedl¨ nder 6. 103. 53 – 57. Org. 713. Soc. Friedl¨ nder 2.. Ting-Chia Huang. 45 (1923) 1816. Dyron. Zuidam.. R. 1942. EP 0 417 829. Davis. 1977 (A. Soc. 603. US 4 410 503. 1937 (H. Snamprogetti. 11. v. Org. 86. Lagana. Functional Finishes. Rev. Coll. pp. Koshino: Fertilizer Technology & Use. in M. VIII. 1993 (T. Synth. 80. D. Engl. 73. 30 (1884) no. Chem. Schweizer. 3 (1964) 260. C. 100. 48 – 327. Justus Liebigs Ann. Ges. 1908. GB 1 560 174. Kurzer. 102. J.) 85 (1978) no. 32 – 37. Wiedemann. Savant. Lagana. Saxena. Environ. Bruls. F. 55. New York 1983. J. Chem. Mann. L. 1956 (Mackey). Douwes). M. Snamprogetti. III. Escherich. Indian J. A. 2. 69 (1973) no. L. 3.). J. US 2 390 253. Dong-Hwang Chen. Houben-Weyl. 1059. Coleman. K. 3 (1923) 95. Du Pont. 70. Blanchard. A. (Leningrad) 42 (1969) no. Saviano. DE 205 662. Davis).Y. Bayer. 64. News 28 (1983) no. Chem. Lewin. Davies. R. 1901. Friedl¨ nder 16. 72. US 1 785 730. Prakt. 1980 (V. VIII. Am. W. 296 (1991) April. Justus a Liebigs Ann. Soc. 106. Ber. Reed. Ges. 831 – 833 (Eng. 96. a 99. 1978 (G. J. 68. 15 (1950) 471. Justus Liebigs Ann. Angew. A. Prakt. M. K. Chem. 88. Ges. Hentschel. 74 (1850) 14. Krishnan. 67. Houben-Weyl. K. Granelli). L. Seances Acad. 62. van Nassau. 131 (1864) 252. DE 216 666. Bonetti). Michler. Baeyer. XXVII/80. Sello (eds. Friedl¨ nder 6. M. Fleischer. E. M. H. Conf. Dtsch. F. 62 – 66. Chem. W. 499. pp. 27 – 35. 85. 80 (1851) 347. 75. American Cyanamid. 97. 71 (1849) 329. Geneva. McKay. J. W. 1940. a BASF. 53. DE 493 811. Dirksen. GB 1 470 489. 107. 151.
121. 1953. Ges. A. BASF. 139. H. Petersen). 132. 92 (1961) 79. 149. DE 859 019. Text. Kunststoffe 37 (1947) 165. 243 – 292. 92 (1961) 42. A. Dtsch. H. Trav. Scheuermann. L. J. A. H. 119. Synthesis 1973. Rauter. Chim. H. J. VIII. W¨ rner). BASF. 111. Res. H. o 153. Chem. H. Test. Chem. Justus Liebigs Ann. Chem. DE 1 231 247. G. 10th. Zigeuner. 1953. C. 170. 1977. G. 144. BASF. 1962 (H. Einhorn. M¨ ller von Blumencron. 123. H. Chem. 157. Dtsch. Ges. 142. Ber. G. H. 79 (1967) 1009. 10 (1956) 244. H. J. Paquin. Chem. GB 1 077 344. 1956 (B. Pauli. 1946. H. 70 (1948) 3795. Chem. von Reibnitz. R. Amende). Fikentscher). G. Res. M. Monatsh. 125. von Reibnitz). Burke). Chem. Fikentscher). Kem. 117. Am. Ztg. 18 (1885) 516. 167. Sauter. 146. BASF. BASF. R. Bonath. Petersen. 147 (1868) 162. Sakaki). Chem. Petersen in: Kunststoff-Jahrbuch. 40 (1970) 335. J. BASF. Y. Ogata. Petersen. W. Lemaitre. Growe. 16 (1961) 646. R. H. o Dtsch. Wischin. Bull. 73 (1951) 2735. H. US 2 304 624. Pays-Bas 76 (1957) 919. H. Acta Chem. 160. 1980 (H. Chem. E. 95 (1971) 692. Willersinn. 134. Petersen. E. 1959. Petersen. Angew. Petersen. 1960 (H. (1955) 1625. 122. H. 1966. C. A. I. DE 1 020 024. DE 1 049 572. Klug. 1959 (H. Chem. Sumitomo Chem. Chem. Mitsubishi Chem. Soc. 155. Behrens. Synthesis 1973. Jung. Brandeis. 154. J. F. DE 1 543 201. 63 (1954) 182. 1459. W. 164. 51 (1947) 369. Smets. 37 (1967) 264. 1961. Paquin. Ztg. Soc. Ges.. 162. Petersen. 127. Eckenroth. Monatsh. Ges. R. Petersen. Chem. 72 (1953) 88. Belg. Ind. W¨ rner). H. Wilhelm Pansegrau Verlag. Ges. 46. G. 1965 (M. Glutz. Landquist. p. Text. Societe Nobel Francaise. Acta 52 (1969) 1976. DE 1 123 334. 165. Acta 52 (1969) 1985. 1962 (H. Wilhelmi. Atkinson. 75 (1953) 574. (1953) 4779. Einhorn. 41 (1971) 239. Chem. Scand. W¨ rner). 151. Dtsch. 92 (1961) 31. Textilveredlung 2 (1967) 744. Chim. Fikentscher). o 152. US 3 190 741. Kv´ ton. Textilveredlung 2 (1967) 243. Burke. Chem. Hamburger. 169. Scheuermann. G. Chem. H. Bischoff. DE 2 757 220. L. Soc. 126. Reol. Zollinger. US 2 649 381. 1962 (H. J.. Zentralbl. N. 69 (1967) 2136. Petersen). 136. G. M. H. Rundsch. BASF. Talet). Hanousek. 140. Scheuermann). Co. Scheuermann). Zigeuner. Text. Chem. Chem. Zentralbl. Nischk. Brandeis. 129. Bettelheim. R. Hart. 110. Ber. Soc. Chemische Werke H¨ ls. Justus Liebigs Ann. Eng. Tidskr. A. Textilveredlung 3 (1968) 160. DE 962 119. A. H. 1942 (W. Chem. 147. Bull. Ugelstadt. A. J. H. Chem. 118. 1952 ¸ (P. Belg. Soc. 361 (1908) 122. EP 0 002 794. H. CH 478 287. Ind. US 4 220 751. R. 128. Ber. 166. 1980 (H. 60 (1948) 208. 11 (1936) 248. C. Melliand Textilber. 1965. H. Bump. A.Urea 109. US 2 436 355. 74 (1952) 2713. J. DE 1 223 843. Jpn. J. 43 (1962) 380. A. 148. DE 910 475. Lintner. 135. Petersen. H. 43 (1910) 1984. H. 35 (1902) 3437. Smythe. 1962 (T. Trav. 159. Lynch. Cedwall. Petersen. Phys. A. 254. 161. Peterson et al. DuPont. 1951 (H. 35 143. 112. 1977. Petersen. Brandeis. ed. Chem. 76 (1964) 909. Zigeuner. Angew. Chem. H. Chem. Smythe. H. 72 (1950) 3622. Sven. 63 (1930) 2063. 113. L. BASF. T. US 4 219 494. A. Soc. BASF. 96 (1965) 1950. o (1955) 702. Petersen. 1963 (J. DuPont. H. 133. DuPont. 115. Chim. 890. Ber. US 2 731 472. K. 130. 1942 (W. de Jonge. 116. Wilm. 173. Bull. J. H. u Pfaff. B. Petersen. Dtsch. Kadowaki. Chim. 114. 131. 1941 (J. B. Monatsh. Biltz. GB 1 241 580. 661. Hamburger. Bille. BASF. Trimborn). 158. 95 (1971) 625. Chim. M. de Jong. 168. Chem. J. Zentralbl. H. Steinbrink. 137. M. A. Chem. A. H. J. Okano. Fischer. Monatsh. BASF. J. BASF. 1968 (H. 63 (1954)182. Eugster. 44 (1952) 333. 172. H. J. 145. 120. Burke). EP 0 002 793. H. Angew. Helv. Petersen. Textilveredlung 3 (1968) 51. BASF. Petersen. J. Berlin 1968. H. 163. Ber. 141. 160. Chem. Zigeuner. Chem. E. R. Listy 48 e (1954) 1205. Petersen. 60 (1948) 267. Chim. A. III. Hamamoto. 9 (1955) 1127. (1936 II)3535. C. Scheuermann.). 1977. 124. US 3 322 528. A. 41 (1908) 24. P. W. 150. Helv. US 2 321 989. Am. Houben-Weyl. Chem. 1981 (H. . Petersen. 1957 u (H. W. 49 (1955) 63. 156. J. 138. DE 1 230 805. Bach. Am. G. Res. Reol. BASF. Willersinn. Y. Petersen. Pays-Bas 71 (1952) 643. Oshima). E. US 4 243 797.. DE 1 081 482. 11 (1957) 776. DE 1 067 210. de Jonge. I. Zollinger. Petersen. Gardziella. von Hedenstr¨ m. US 2 638 434. BASF. B. Zentralbl. 171.
36 Urea Urea Resins → Amino Resins Vaccines → Immunotherapy and Vaccines Vacuum Coating → Thin Films .
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